Polymer blends from interpolymers of ethylene/alpha-olefin with improved compatibility

ABSTRACT

Disclosed herein are polymer blends comprising at least one ethylene/α-olefin interpolymer and two different polyolefins which can be homopolymers. The ethylene/α-olefin interpolymers are block copolymers comprising at least a hard block and at least a soft block. In some embodiments, the ethylene/α-olefin interpolymer can function as a compatibilizer between the two polyolefins which may not be otherwise compatible. Methods of making the polymer blends and molded articles made from the polymer blends are also described.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application No.60/717,825, filed Sep. 16, 2005, which further claims priority to PCTApplication No. PCT/US2005/008917, filed on Mar. 17, 2005, which in turnclaims priority to U.S. Provisional Application No. 60/553,906, filedMar. 17, 2004. For purposes of U.S. patent practice, the contents of theprovisional applications and the PCT application are herein incorporatedby reference in their entirety.

FIELD OF THE INVENTION

This invention relates to polymer blends made from an ethylene/a-olefininterpolymer and at least two polyolefins, methods of making the blends,and articles made from the blends.

BACKGROUND OF THE INVENTION

Multiphase polymer blends are of major economic importance in thepolymer industry. Some examples of the multiphase polymer blends involvethe impact modification of thermoplastics by the dispersion of rubbermodifiers into the thermoplastic matrixes. In general, commercialpolymer blends consist of two or more polymers combined with smallamounts of a compatibilizer or an interfacial agent. Generally, thecompatibilizers or interfacial agents are block or graft copolymerswhich can promote the forming of small rubber domains in the polymerblends so as to improve their impact strength.

In many applications, blends of polypropylene (PP) and ethylene/α-olefincopolymers are used. The ethylene/α-olefin copolymer functions as arubber modifier in the blends and provides toughness and good impactstrength. In general, the impact efficiency of the ethylene/α-olefincopolymer may be a function of a) the glass transition (Tg) of therubber modifier, b) the adhesion of the rubber modifier to thepolypropylene interface, and c) the difference in the viscosities of therubber modifier and polypropylene. The Tg of the rubber modifier can beimproved by various methods such as decreasing the crystallinity of theα-olefin component. Similarly, the viscosity difference of the rubbermodifier and polypropylene can be optimized by various techniques suchas adjusting the molecular weight and molecular weight distribution ofthe rubber modifier. For ethylene/higher alpha-olefin (HAO) copolymers,the interfacial adhesion of the copolymer can be increased by increasingthe amount of the HAO. However, when the amount of the HAO is greaterthan 55 mole % in the ethylene/HAO copolymer, the polypropylene becomemiscible with the ethylene/HAO copolymer and they form a single phaseand there are no small rubber domains. Therefore, the ethylene/HAOcopolymer with greater than 55 mole % of HAO has a limited utility as animpact modifier.

For thermoplastic vulcanizates (TPV's) where the rubber domains arecrosslinked, it is desirable to improve properties such as compressionset and tensile strength. These desirable properties can be improved bydecreasing the average rubber particle size. During the dynamicvulcanization step of TPV's comprising polypropylene and a polyolefininterpolymer such as ethylene/alpha-olefin/diene terpolymers (e.g.,ethylene/propylene/diene terpolymer (EPDM)), there must be a balance ofcompatibility of the terpolymer with the polypropylene. In general, EPDMhas a good compatibility with polypropylene, but the compatibility canonly be marginally improved with increasing propylene level in EPDM.

Despite the availability of a variety of polymer blends, there is a needto continue to develop polymer blends with improved properties.

SUMMARY OF THE INVENTION

The aforementioned needs are met by various aspects of the invention. Inone aspect, the invention relates to polymer blends comprising: (i) afirst polyolefin; (ii) a second polyolefin; and (iii) anethylene/α-olefin interpolymer, wherein the first polyolefin, the secondpolyolefin and the ethylene/α-olefin interpolymer are different. Theterm “different” when referring to two polyolefins means that the twopolyolefins differ in composition (comonomer type, comonomer content,etc.), structure, properties, or a combination thereof. For example, ablock ethylene/octene copolymer is different than a randomethylene/octene copolymer, even if they have the same amount ofcomonomers. A block ethylene/octene copolymer is different than anethylene/butane copolymer, regardless of whether it is a random or blockcopolymer or whether it has the same comonomer content. Two polyolefinsalso are considered different if they have a different molecular weight,even though they have the same structure and composition. Moreover, arandom homogeneous ethylene/octene copolymer is different than a randomheterogenous ethylene/octene copolymer, even if all other parameters maybe the same.

The ethylene/α-olefin interpolymer used in the polymer blends has one ormore of the following characterstics:

(a) has a Mw/Mn from about 1.7 to about 3.5, at least one melting point,Tm, in degrees Celsius, and a density, d, in grams/cubic centimeter,wherein the numerical values of Tm and d correspond to the relationship:T _(m)>−2002.9+4538.5(d)−2422.2(d)², or

(b) has a Mw/Mn from about 1.7 to about 3.5, and is characterized by aheat of fusion, ΔH in J/g, and a delta quantity, ΔT, in degrees Celsiusdefined as the temperature difference between the tallest DSC peak andthe tallest CRYSTAF peak, wherein the numerical values of ΔT and ΔH havethe following relationships:ΔT>−0.1299(ΔH)+62.81 for ΔH greater than zero and up to 130 J/g,ΔT≧48° C. for ΔH greater than 130 J/g,wherein the CRYSTAF peak is determined using at least 5 percent of thecumulative polymer, and if less than 5 percent of the polymer has anidentifiable CRYSTAF peak, then the CRYSTAF temperature is 30° C.; or

(c) is characterized by an elastic recovery, Re, in percent at 300percent strain and I cycle measured with a compression-molded film ofthe ethylene/α-olefin interpolymer, and has a density, d, in grams/cubiccentimeter, wherein the numerical values of Re and d satisfy thefollowing relationship when the ethylene/α-olefin interpolymer issubstantially free of a cross-linked phase:Re>1481-1629(d); or

(d) has a molecular fraction which elutes between 40° C. and 130° C.when fractionated using TREF, characterized in that the fraction has amolar comonomer content of at least 5 percent higher than that of acomparable random ethylene interpolymer fraction eluting between thesame temperatures, wherein said comparable random ethylene interpolymerhas the same comonomer(s) and a melt index, density, and molar comonomercontent (based on the whole polymer) within 10 percent of that of theethylene/α-olefin interpolymer; or

(e) is characterized by a storage modulus at 25° C., G′(25° C.), and astorage modulus at 100° C., G′(100° C.), wherein the ratio of G′(25° C.)to G′(100° C.) is from about 1:1 to about 10:1.

In one embodiment, the ethylene/α-olefin interpolymer has a Mw/Mn fromabout 1.7 to about 3.5, at least one melting point, Tm, in degreesCelsius, and a density, d, in grams/cubic centimeter, wherein thenumerical values of Tm and d correspond to the relationship:Tm≧858.91-1825.3(d)+1112.8(d)².

In another embodiment, the ethylene/α-olefin interpolymer has a Mw/Mnfrom about 1.7 to about 3.5 and is characterized by a heat of fusion, ΔHin J/g, and a delta quantity, ΔT, in degrees Celsius defined as thetemperature difference between the tallest DSC peak and the tallestCRYSTAF peak, wherein the numerical values of ΔT and ΔH have thefollowing relationships:ΔT>−0.1299(ΔH)+62.81 for ΔH greater than zero and up to 130 J/g,ΔT≧48° C. for ΔH greater than 130 J/g,wherein the CRYSTAF peak is determined using at least 5 percent of thecumulative polymer, and if less than 5 percent of the polymer has anidentifiable CRYSTAF peak, then the CRYSTAF temperature is 30° C.

In one embodiment, the ethylene/α-olefin interpolymer is characterizedby an elastic recovery, Re, in percent at 300 percent strain and I cyclemeasured with a compression-molded film of the ethylene/α-olefininterpolymer, and has a density, d, in grams/cubic centimeter, whereinthe numerical values of Re and d satisfy the following relationship whenthe ethylene/α-olefin interpolymer is substantially free of across-linked phase: Re>1481-1629(d), Re>1491-1629(d), Re>1501-1629(d),or Re>1511-1629(d).

In some embodiments, the polymer blend comprises (i) a first polyolefin;(ii) a second polyolefin; and (iii) an ethylene/α-olefin interpolymer,wherein the first polyolefin, the second polyolefin and theethylene/α-olefin interpolymer are different. In one embodiment, theethylene/α-olefin interpolymer has:

(a) at least one molecular fraction which elutes between 40° C. and 130°C. when fractionated using TREF, characterized in that the fraction hasa block index of at least 0.5 and up to about 1 and a molecular weightdistribution, Mw/Mn, greater than about 1.3 or

(b) an average block index greater than zero and up to about 1.0 and amolecular weight distribution, Mw/Mn, greater than about 1.3.

In other embodiments, the ethylene/α-olefin interpolymer has a molecularfraction which elutes between 40° C. and 130° C. when fractionated usingTREF, characterized in that the fraction has a molar comonomer contentof at least 5 percent higher than that of a comparable random ethyleneinterpolymer fraction eluting between the same temperatures, whereinsaid comparable random ethylene interpolymer has the same comonomer(s)and a melt index, density, and molar comonomer content (based on thewhole polymer) within 10 percent of that of the ethylene/α-olefininterpolymer.

In some embodiments, the ethylene/α-olefin interpolymer is characterizedby a storage modulus at 25° C., G′(25° C.), and a storage modulus at100° C., G′(100° C.), wherein the ratio of G′(25° C.) to G′(100° C.) isfrom about 1:1 to about 10:1.

In one embodiment, the ethylene/α-olefin interpolymer is a random blockcopolymer comprising at least a hard block and at least a soft block. Inanother embodiment, ethylene/α-olefin interpolymer is a random blockcopolymer comprising multiple hard blocks and multiple soft blocks, andthe hard blocks and soft blocks are random distributed in a polymericchain.

In one embodiment, the α-olefin in the polymer blends provided herein isa C4-40 α-olefin. In another embodiment, the α-olefin is styrene,propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, norbornene,1-decene, 1,5-hexadiene, or a combination thereof.

In some embodiments, the ethylene/α-olefin interpolymer has a melt indexin the range of about 0.1 to about 2000 g/10 minutes, about 1 to about1500 g/10 minutes, about 2 to about 1000 g/10 minutes, or about 5 toabout 500 g/10 minutes measured according to ASTM D-1238, Condition 190°C./2.16 kg.

In some embodiments, the amount of the ethylene/α-olefin interpolymer inthe polymer blends provided herein is from about 0.5% to about 99%, fromabout 1% to about 50%, from about 2 to about 25%, from about 3 to about15%, or from about 5 to about 10% by weight of the total composition.

In other embodiments, the ethylene/α-olefin interpolymer contains softsegments having an α-olefin content greater than 30 mole %, greater than35 mole %, greater than 40 mole %, greater than 45 mole % or greaterthan 55 mole %. In one embodiment, the elastomeric polymer contains softsegments having an α-olefin content greater than 55 mole %.

In some embodiments, the ethylene/α-olefin interpolymer in the polymerblend comprises an elastomeric polymer having an ethylene content offrom 5 to 95 mole percent, a diene content of from 5 to 95 mole percent,and an α-olefin content of from 5 to 95 mole percent. The α-olefin inthe elastomeric polymer can be a C4-40 α-olefin.

In some embodiments, the amount of the first polyolefin in the polymerblends is from about 0.5 to about 99 wt % of the total weight of thepolymer blend. In some embodiments, the amount of the second polyolefinin the polymer blends is from about 0.5 to about 99 wt % of the totalweight of the polymer blend.

In one embodiment, the first polyolefin is an olefin homopolymer, suchas polypropylene. The polypropelene for use herein includes, but is notlimited to a low density polypropylene (LDPP), high densitypolypropylene (HDPP), high melt strength polypropylene (HMS-PP), highimpact polypropylene (HIPP), isotactic polypropylene (iPP), syndiotacticpolypropylene (sPP) and a combination thereof. In one embodiment, thepolypropylene is isotactic polypropylene.

In another embodiment, the second polyolefin is an olefin copolymer, anolefin terpolymer or a combination thereof. The olefin copolymer can bederived from ethylene and a monoene having 3 or more carbon atoms.Exemplary olefin copolymers are ethylene/alpha-olefin (EAO) copolymersand ethylene/propylene copolymers (EPM). The olefin terpolymer for usein the polymer blends can be derived from ethylene, a monoene having 3or more carbon atoms, and a diene and include, but are not limited to,ethylene/alpha-olefin/diene terpolymer (EAODM) andethylene/propylene/diene terpolymer (EPDM). In one embodiment, thesecond polyolefin is a vulcanizable rubber.

In some embodiments, the polymer blend further comprises at least oneadditive, such as a slip agent, an anti-blocking agent, a plasticizer,an antioxidant, a UV stabilizer, a colorant or pigment, a filler, alubricant, an antifogging agent, a flow aid, a coupling agent, across-linking agent, a nucleating agent, a surfactant, a solvent, aflame retardant, an antistatic agent, or a combination thereof.

Also provided herein are molded articles comprising the polymer blend.Exemplary molded articles include a tire, a hose, a belt, a gasket, ashoe sole, a molding or a molded part. Such molded articles can beprepared by injection molding, extrusion blow molding or injection blowmolding. In one embodiment, the molded article is foamed by a chemicalor physical blowing agent.

Further provided herein are sheet articles, profile articles and filmarticles comprising at least a layer comprising the polymer blendprovided herein. In one embodiment, the sheet article is prepared byextrusion or calendering. In another embodiment, the sheet article isfoamed by a chemical or physical blowing agent. Also provided herein isa thermoformed article comprising the sheet. In certain embodiments, theprofile and film articles can be prepared by extrusion.

Also provided herein are methods of making a polymer blend, comprisingblending a first polyolefin, a second polyolefin and anethylene/α-olefin interpolymer, wherein the first polyolefin, the secondpolyolefin and the ethylene/α-olefin interpolymer are different. Theethylene/α-olefin interpolymer used in the polymer blends is asdescribed above and elsewhere herein.

Additional aspects of the invention and characteristics and propertiesof various embodiments of the invention become apparent with thefollowing description.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the melting point/density relationship for the inventivepolymers (represented by diamonds) as compared to traditional randomcopolymers (represented by circles) and Ziegler-Natta copolymers(represented by triangles).

FIG. 2 shows plots of delta DSC-CRYSTAF as a function of DSC MeltEnthalpy for various polymers. The diamonds represent randomethylene/octene copolymers; the squares represent polymer examples 1-4;the triangles represent polymer examples 5-9; and the circles representpolymer examples 10-19. The “X” symbols represent polymer examplesA*-F*.

FIG. 3 shows the effect of density on elastic recovery for unorientedfilms comprising inventive interpolymers(represented by the squares andcircles) and traditional copolymers (represented by the triangles whichare various Dow AFFINITY® polymers). The squares represent inventiveethylene/butene copolymers; and the circles represent inventiveethylene/octene copolymers.

FIG. 4 is a plot of octene content of TREF fractionatedethylene/1-octene copolymer fractions versus TREF elution temperature ofthe fraction for the polymer of Example 5 (represented by the circles)and Comparative Examples E* and F* (represented by the “X” symbols). Thediamonds represent traditional random ethylene/octene copolymers.

FIG. 5 is a plot of octene content of TREF fractionatedethylene/1-octene copolymer fractions versus TREF elution temperature ofthe fraction for the polymer of Example 5 (curve 1) and for ComparativeExample F* (curve 2). The squares represent Example F*; and thetriangles represent Example 5.

FIG. 6 is a graph of the log of storage modulus as a function oftemperature for comparative ethylene/1-octene copolymer (curve 2) andpropylene/ethylene-copolymer (curve 3) and for two ethylene/1-octeneblock copolymers of the invention made with differing quantities ofchain shuttling agent (curves 1).

FIG. 7 shows a plot of TMA (1 mm) versus flex modulus for some inventivepolymers (represented by the diamonds), as compared to some knownpolymers. The triangles represent various Dow VERSIFY® polymers; thecircles represent various random ethylene/styrene copolymers; and thesquares represent various Dow AFFINITY® polymers.

FIG. 8 is a transmission electron micrograph of a mixture ofpolypropylene and an ethylene/octene block copolymer of Example 20.

FIG. 9 is a transmission electron micrograph of a mixture ofpolypropylene and a random ethylene/octene copolymer (ComparativeExample A¹).

FIG. 10 is a transmission electron micrograph of a mixture ofpolypropylene, an ethylene-octene block copolymer (Example 20), and arandom ethylene-octene copolymer (Comparative Example A¹).

DETAILED DESCRIPTION OF THE INVENTION

General Definitions

“Polymer” means a polymeric compound prepared by polymerizing monomers,whether of the same or a different type. The generic term “polymer”embraces the terms “homopolymer,” “copolymer,” “terpolymer” as well as“interpolymer.”

“Interpolymer” means a polymer prepared by the polymerization of atleast two different types of monomers. The generic term “interpolymer”includes the term “copolymer” (which is usually employed to refer to apolymer prepared from two different monomers) as well as the term“terpolymer” (which is usually employed to refer to a polymer preparedfrom three different types of monomers). It also encompasses polymersmade by polymerizing four or more types of monomers.

The term “ethylene/α-olefin interpolymer” generally refers to polymerscomprising ethylene and an α-olefin having 3 or more carbon atoms.Preferably, ethylene comprises the majority mole fraction of the wholepolymer, i.e., ethylene comprises at least about 50 mole percent of thewhole polymer. More preferably ethylene comprises at least about 60 molepercent, at least about 70 mole percent, or at least about 80 molepercent, with the substantial remainder of the whole polymer comprisingat least one other comonomer that is preferably an α-olefin having 3 ormore carbon atoms. For many ethylene/octene copolymers, the preferredcomposition comprises an ethylene content greater than about 80 molepercent of the whole polymer and an octene content of from about 10 toabout 15, preferably from about 15 to about 20 mole percent of the wholepolymer. In some embodiments, the ethylene/α-olefin interpolymers do notinclude those produced in low yields or in a minor amount or as aby-product of a chemical process. While the ethylene/α-olefininterpolymers can be blended with one or more polymers, the as-producedethylene/α-olefin interpolymers are substantially pure and oftencomprise a major component of the reaction product of a polymerizationprocess.

The ethylene/α-olefin interpolymers comprise ethylene and one or morecopolymerizable α-olefin comonomers in polymerized form, characterizedby multiple blocks or segments of two or more polymerized monomer unitsdiffering in chemical or physical properties. That is, theethylene/α-olefin interpolymers are block interpolymers, preferablymulti-block interpolymers or copolymers. The terms “interpolymer” andcopolymer” are used interchangeably herein. In some embodiments, themulti-block copolymer can be represented by the following formula:(AB)_(n)where n is at least 1, preferably an integer greater than 1, such as 2,3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, or higher, “A”represents a hard block or segment and “B” represents a soft block orsegment. Preferably, As and Bs are linked in a substantially linearfashion, as opposed to a substantially branched or substantiallystar-shaped fashion. In other embodiments, A blocks and B blocks arerandomly distributed along the polymer chain. In other words, the blockcopolymers usually do not have a structure as follows.AAA-AA-BBB-BBIn still other embodiments, the block copolymers do not usually have athird type of block, which comprises different comonomer(s). In yetother embodiments, each of block A and block B has monomers orcomonomers substantially randomly distributed within the block. In otherwords, neither block A nor block B comprises two or more sub-segments(or sub-blocks) of distinct composition, such as a tip segment, whichhas a substantially different composition than the rest of the block.

The multi-block polymers typically comprise various amounts of “hard”and “soft” segments. “Hard” segments refer to blocks of polymerizedunits in which ethylene is present in an amount greater than about 95weight percent, and preferably greater than about 98 weight percentbased on the weight of the polymer. In other words, the comonomercontent (content of monomers other than ethylene) in the hard segmentsis less than about 5 weight percent, and preferably less than about 2weight percent based on the weight of the polymer. In some embodiments,the hard segments comprises all or substantially all ethylene. “Soft”segments, on the other hand, refer to blocks of polymerized units inwhich the comonomer content (content of monomers other than ethylene) isgreater than about 5 weight percent, preferably greater than about 8weight percent, greater than about 10 weight percent, or greater thanabout 15 weight percent based on the weight of the polymer. In someembodiments, the comonomer content in the soft segments can be greaterthan about 20 weight percent, greater than about 25 weight percent,greater than about 30 weight percent, greater than about 35 weightpercent, greater than about 40 weight percent, greater than about 45weight percent, greater than about 50 weight percent, or greater thanabout 60 weight percent.

The soft segments can often be present in a block interpolymer fromabout 1 weight percent to about 99 weight percent of the total weight ofthe block interpolymer, preferably from about 5 weight percent to about95 weight percent, from about 10 weight percent to about 90 weightpercent, from about 15 weight percent to about 85 weight percent, fromabout 20 weight percent to about 80 weight percent, from about 25 weightpercent to about 75 weight percent, from about 30 weight percent toabout 70 weight percent, from about 35 weight percent to about 65 weightpercent, from about 40 weight percent to about 60 weight percent, orfrom about 45 weight percent to about 55 weight percent of the totalweight of the block interpolymer. Conversely, the hard segments can bepresent in similar ranges. The soft segment weight percentage and thehard segment weight percentage can be calculated based on data obtainedfrom DSC or NMR. Such methods and calculations are disclosed in aconcurrently filed U.S. patent application Ser. No. ______ (insert whenknown), Attorney Docket No. 385063-999558, entitled “Ethylene/a-OlefinBlock Interpolymers”, filed on Mar. 15, 2006, in the name of Colin L. P.Shan, Lonnie Hazlitt, et. al. and assigned to Dow Global TechnologiesInc., the disclose of which is incorporated by reference herein in itsentirety.

The term “crystalline” if employed, refers to a polymer that possesses afirst order transition or crystalline melting point (Tm) as determinedby differential scanning calorimetry (DSC) or equivalent technique. Theterm may be used interchangeably with the term “semicrystalline”. Theterm “amorphous” refers to a polymer lacking a crystalline melting pointas determined by differential scanning calorimetry (DSC) or equivalenttechnique.

The term “multi-block copolymer” or “segmented copolymer” refers to apolymer comprising two or more chemically distinct regions or segments(referred to as “blocks”) preferably joined in a linear manner, that is,a polymer comprising chemically differentiated units which are joinedend-to-end with respect to polymerized ethylenic functionality, ratherthan in pendent or grafted fashion. In a preferred embodiment, theblocks differ in the amount or type of comonomer incorporated therein,the density, the amount of crystallinity, the crystallite sizeattributable to a polymer of such composition, the type or degree oftacticity (isotactic or syndiotactic), regio-regularity orregio-irregularity, the amount of branching, including long chainbranching or hyper-branching, the homogeneity, or any other chemical orphysical property. The multi-block copolymers are characterized byunique distributions of both polydispersity index (PDI or Mw/Mn), blocklength distribution, and/or block number distribution due to the uniqueprocess making of the copolymers. More specifically, when produced in acontinuous process, the polymers desirably possess PDI from 1.7 to 2.9,preferably from 1.8 to 2.5, more preferably from 1.8 to 2.2, and mostpreferably from 1.8 to 2.1. When produced in a batch or semi-batchprocess, the polymers possess PDI from 1.0 to 2.9, preferably from 1.3to 2.5, more preferably from 1.4 to 2.0, and most preferably from 1.4 to1.8.

The term “compatibilizer” refers to a polymer that, when added to animmiscible polymer blend, can increase the miscibility of the twopolymers resulting in an increased stability in the blend. In someembodiments, the compatabilizer can reduce the average domain size by atleast 20%, more preferably at least 30%, at least 40%, or at least 50%,when about 15 weight percent of the compatibilizer is added to theblend. In other embodiments, the compatabilizer can increase themiscibility of two or more polymers by at least 10%, more preferably atleast 20%, at least 30%, at least 40%, or at least 50%, when about 15weight percent of the compatibilizer is added to the blend.

The term “immiscible” refers to two polymers when they do not form ahomogenous mixture after being mixed. In other words, phase separationoccurs in the mixture. One method to quantify the immiscibility of twopolymers is to use Hildbrand's solubility parameter which is a measureof the total forces holding the molecules of a solid or liquid together.Every polymer is characterized by a specific value of solubilityparameter, although it is not always available. Polymers with similarsolubility parameter values tend to be miscible. On the other hand,those with significantly different solubility parameters tend to beimmiscible, although there are many exceptions to this behavior.Discussions of solubility parameter concepts are presented in (1)Encyclopedia of Polymer Science and Technology, Interscience, New York(1965), Vol. 3, pg. 833; (2) Encyclopedia of Chemical Technology,Interscience, New York (1971), Supp. Vol., pg. 889; and (3) PolymerHandbook, 3rd Ed., J. Brandup and E. H. Immergut (Eds.), (1989), JohnWiley & Sons “Solubility Parameter Values,” pp. VII-519, which areincorporated by reference in their entirety herein.

The term “interfacial agent” refers to an additive that reduces theinterfacial energy between phase domains.

The term “olefin” refers to a hydrocarbon contains at least onecarbon-carbon double bond.

The term “thermoplastic vulcanizate” (TPV) refers to an engineeringthermoplastic elastomer in which a cured elastomeric phase is dispersedin a thermoplastic matrix. The TPV generally comprises at least onethermoplastic material and at least one cured (i.e., cross-linked)elastomeric material. In some embodiments, the thermoplastic materialforms the continuous phase, and the cured elastomer forms the discretephase; that is, domains of the cured elastomer are dispersed in thethermoplastic matrix. In other embodiments, the domains of the curedelastomer are fully and uniformly dispersed with the average domain sizein the range from about 0.1 micron to about 100 micron, from about 1micron to about 50 microns; from about 1 micron to about 25 microns;from about 1 micron to about 10 microns, or from about 1 micron to about5 microns. In certain embodiments, the matrix phase of the TPV ispresent by less than about 50% by volume of the TPV, and the dispersedphase is present by at least about 50% by volume of the TPV. In otherwords, the crosslinked elastomeric phase is the major phase in the TPV,whereas the thermoplastic polymer is the minor phase. TPVs with suchphase composition can have good compression set. However, TPVs with themajor phase being the thermoplastic polymer and the minor phase beingthe cross-linked elastomer may also be made. Generally, the curedelastomer has a portion that is insoluble in cyclohexane at 23° C. Theamount of the insoluble portion is preferably more than about 75% orabout 85%. In some cases, the insoluble amount is more than about 90%,more than about 93%, more than about 95% or more than about 97% byweight of the total elastomer.

In the following description, all numbers disclosed herein areapproximate values, regardless whether the word “about” or “approximate”is used in connection therewith. They may vary by 1 percent, 2 percent,5 percent, or, sometimes, 10 to 20 percent. Whenever a numerical rangewith a lower limit, R^(L) and an upper limit, R^(U), is disclosed, anynumber falling within the range is specifically disclosed. Inparticular, the following numbers within the range are specificallydisclosed: R=R^(L)+k*(R^(U)−R^(L)), wherein k is a variable ranging from1 percent to 100 percent with a 1 percent increment, i.e., k is 1percent, 2 percent, 3 percent, 4 percent, 5 percent, . . . , 50 percent,51 percent, 52 percent, . . . , 95 percent, 96 percent, 97 percent, 98percent, 99 percent, or 100 percent. Moreover, any numerical rangedefined by two R numbers as defined in the above is also specificallydisclosed.

Embodiments of the invention provide polymer blends comprising at leastone ethylene/α-olefin interpolymer and at least two polyolefins. Thepolymer blends with improved compatibility possess unique physical andmechanical properties that are suitable for making molded articles for avariety of applications. The ethylene/α-olefin interpolymer can improvethe compatibility of the two polyolefins which otherwise may berelatively incompatible. In other words, the interpolymer is acompatibilizer between two or more polyolefins.

Ethylene/α-Olefin Interpolymers

The ethylene/α-olefin interpolymers used in embodiments of the invention(also referred to as “inventive interpolymer” or “inventive polymer”)comprise ethylene and one or more copolymerizable α-olefin comonomers inpolymerized form, characterized by multiple blocks or segments of two ormore polymerized monomer units differing in chemical or physicalproperties (block interpolymer), preferably a multi-block copolymer. Theethylene/α-olefin interpolymers are characterized by one or more of theaspects described as follows.

In one aspect, the ethylene/α-olefin interpolymers used in embodimentsof the invention have a M_(w)/M_(n) from about 1.7 to about 3.5 and atleast one melting point, T_(m), in degrees Celsius and density, d, ingrams/cubic centimeter, wherein the numerical values of the variablescorrespond to the relationship:T _(m)>−2002.9+4538.5(d)−2422.2(d)², and preferablyT _(m)≧6288.1+13141(d)−6720.3(d)², and more preferablyT _(m)≧858.91−1825.3(d)+1112.8(d)².

Such melting point/density relationship is illustrated in FIG. 1. Unlikethe traditional random copolymers of ethylene/α-olefins whose meltingpoints decrease with decreasing densities, the inventive interpolymers(represented by diamonds) exhibit melting points substantiallyindependent of the density, particularly when density is between about0.87 g/cc to about 0.95 g/cc. For example, the melting point of suchpolymers are in the range of about 110° C. to about 130° C. when densityranges from 0.875 g/cc to about 0.945 g/cc. In some embodiments, themelting point of such polymers are in the range of about 115° C. toabout 125° C. when density ranges from 0.875 g/cc to about 0.945 g/cc.

In another aspect, the ethylene/α-olefin interpolymers comprise, inpolymerized form, ethylene and one or more α-olefins and arecharacterized by a ΔT, in degree Celsius, defined as the temperature forthe tallest Differential Scanning Calorimetry (“DSC”) peak minus thetemperature for the tallest Crystallization Analysis Fractionation(“CRYSTAF”) peak and a heat of fusion in J/g, ΔH, and ΔT and ΔH satisfythe following relationships:ΔT>−0.1299(ΔH)+62.81, and preferablyΔT≧−0.1299(ΔH)+64.38, and more preferablyΔT≧−0.1299(ΔH)+65.95,for ΔH up to 130 J/g. Moreover, ΔT is equal to or greater than 48° C.for ΔH greater than 130 J/g. The CRYSTAF peak is determined using atleast 5 percent of the cumulative polymer (that is, the peak mustrepresent at least 5 percent of the cumulative polymer), and if lessthan 5 percent of the polymer has an identifiable CRYSTAF peak, then theCRYSTAF temperature is 30° C., and ΔH is the numerical value of the heatof fusion in J/g. More preferably, the highest CRYSTAF peak contains atleast 10 percent of the cumulative polymer. FIG. 2 shows plotted datafor inventive polymers as well as comparative examples. Integrated peakareas and peak temperatures are calculated by the computerized drawingprogram supplied by the instrument maker. The diagonal line shown forthe random ethylene octene comparative polymers corresponds to theequation ΔT=−0.1299 (ΔH)+62.81.

In yet another aspect, the ethylene/α-olefin interpolymers have amolecular fraction which elutes between 40° C. and 130° C. whenfractionated using Temperature Rising Elution Fractionation (“TREF”),characterized in that said fraction has a molar comonomer contenthigher, preferably at least 5 percent higher, more preferably at least10 percent higher, than that of a comparable random ethyleneinterpolymer fraction eluting between the same temperatures, wherein thecomparable random ethylene interpolymer contains the same comonomer(s),and has a melt index, density, and molar comonomer content (based on thewhole polymer) within 10 percent of that of the block interpolymer.Preferably, the Mw/Mn of the comparable interpolymer is also within 10percent of that of the block interpolymer and/or the comparableinterpolymer has a total comonomer content within 10 weight percent ofthat of the block interpolymer.

In still another aspect, the ethylene/α-olefin interpolymers arecharacterized by an elastic recovery, Re, in percent at 300 percentstrain and 1 cycle measured on a compression-molded film of anethylene/α-olefin interpolymer, and has a density, d, in grams/cubiccentimeter, wherein the numerical values of Re and d satisfy thefollowing relationship when ethylene/α-olefin interpolymer issubstantially free of a cross-linked phase:Re>1481-1629(d); and preferablyRe≧1491-1629(d); and more preferablyRe≧1501-1629(d); and even more preferablyRe≧1511-1629(d).

FIG. 3 shows the effect of density on elastic recovery for unorientedfilms comprising certain inventive interpolymers and traditional randomcopolymers. For the same density, the inventive interpolymers havesubstantially higher elastic recoveries.

In some embodiments, the ethylene/α-olefin interpolymers have a tensilestrength above 10 MPa, preferably a tensile strength≧11 MPa, morepreferably a tensile strength≧13 MPa and/or an elongation at break of atleast 600 percent, more preferably at least 700 percent, highlypreferably at least 800 percent, and most highly preferably at least 900percent at a crosshead separation rate of 11 cm/minute.

In other embodiments, the ethylene/α-olefin interpolymers have (1) astorage modulus ratio, G′(25° C.)/G′(100° C.), of from 1 to 50,preferably from 1 to 20, more preferably from 1 to 10; and/or (2) a 70°C. compression set of less than 80 percent, preferably less than 70percent, especially less than 60 percent, less than 50 percent, or lessthan 40 percent, down to a compression set of 0 percent.

In still other embodiments, the ethylene/α-olefin interpolymers have a70° C. compression set of less than 80 percent, less than 70 percent,less than 60 percent, or less than 50 percent. Preferably, the 70° C.compression set of the interpolymers is less than 40 percent, less than30 percent, less than 20 percent, and may go down to about 0 percent.

In some embodiments, the ethylene/α-olefin interpolymers have a heat offusion of less than 85 J/g and/or a pellet blocking strength of equal toor less than 100 pounds/foot² (4800 Pa), preferably equal to or lessthan 50 lbs/ft² (2400 Pa), especially equal to or less than 5 lbs/ft²(240 Pa), and as low as 0 lbs/ft2 (0 Pa).

In other embodiments, the ethylene/α-olefin interpolymers comprise, inpolymerized form, at least 50 mole percent ethylene and have a 70° C.compression set of less than 80 percent, preferably less than 70 percentor less than 60 percent, most preferably less than 40 to 50 percent anddown to close zero percent.

In some embodiments, the multi-block copolymers possess a PDI fitting aSchultz-Flory distribution rather than a Poisson distribution. Thecopolymers are further characterized as having both a polydisperse blockdistribution and a polydisperse distribution of block sizes andpossessing a most probable distribution of block lengths. Preferredmulti-block copolymers are those containing 4 or more blocks or segmentsincluding terminal blocks. More preferably, the copolymers include atleast 5, 10 or 20 blocks or segments including terminal blocks.

Comonomer content may be measured using any suitable technique, withtechniques based on nuclear magnetic resonance (“NMR”) spectroscopypreferred. Moreover, for polymers or blends of polymers havingrelatively broad TREF curves, the polymer desirably is firstfractionated using TREF into fractions each having an eluted temperaturerange of 10° C. or less. That is, each eluted fraction has a collectiontemperature window of 10° C. or less. Using this technique, said blockinterpolymers have at least one such fraction having a higher molarcomonomer content than a corresponding fraction of the comparableinterpolymer.

In another aspect, the inventive polymer is an olefin interpolymer,preferably comprising ethylene and one or more copolymerizablecomonomers in polymerized form, characterized by multiple blocks (i.e.,at least two blocks) or segments of two or more polymerized monomerunits differing in chemical or physical properties (blockedinterpolymer), most preferably a multi-block copolymer, said blockinterpolymer having a peak (but not just a molecular fraction) whichelutes between 40° C. and 130° C. (but without collecting and/orisolating individual fractions), characterized in that said peak, has acomonomer content estimated by infra-red spectroscopy when expandedusing a full width/half maximum (FWHM) area calculation, has an averagemolar comonomer content higher, preferably at least 5 percent higher,more preferably at least 10 percent higher, than that of a comparablerandom ethylene interpolymer peak at the same elution temperature andexpanded using a full width/half maximum (FWHM) area calculation,wherein said comparable random ethylene interpolymer has the samecomonomer(s) and has a melt index, density, and molar comonomer content(based on the whole polymer) within 10 percent of that of the blockedinterpolymer. Preferably, the Mw/Mn of the comparable interpolymer isalso within 10 percent of that of the blocked interpolymer and/or thecomparable interpolymer has a total comonomer content within 10 weightpercent of that of the blocked interpolymer. The full width/half maximum(FWHM) calculation is based on the ratio of methyl to methylene responsearea [CH₃/CH₂] from the ATREF infra-red detector, wherein the tallest(highest) peak is identified from the base line, and then the FWHM areais determined. For a distribution measured using an ATREF peak, the FWHMarea is defined as the area under the curve between T₁ and T₂, where T₁and T₂ are points determined, to the left and right of the ATREF peak,by dividing the peak height by two, and then drawing a line horizontalto the base line, that intersects the left and right portions of theATREF curve. A calibration curve for comonomer content is made usingrandom ethylene/α-olefin copolymers, plotting comonomer content from NMRversus FWHM area ratio of the TREF peak. For this infra-red method, thecalibration curve is generated for the same comonomer type of interest.The comonomer content of TREF peak of the inventive polymer can bedetermined by referencing this calibration curve using its FWHM methyl :methylene area ratio [CH₃/CH₂] of the TREF peak.

Comonomer content may be measured using any suitable technique, withtechniques based on nuclear magnetic resonance (NMR) spectroscopypreferred. Using this technique, said blocked interpolymers has highermolar comonomer content than a corresponding comparable interpolymer.

Preferably, for interpolymers of ethylene and 1-octene, the blockinterpolymer has a comonomer content of the TREF fraction elutingbetween 40 and 130° C. greater than or equal to the quantity(−0.2013)T+20.07, more preferably greater than or equal to the quantity(−0.2013)T+21.07, where T is the numerical value of the peak elutiontemperature of the TREF fraction being compared, measured in ° C.

FIG. 4 graphically depicts an embodiment of the block interpolymers ofethylene and 1-octene where a plot of the comonomer content versus TREFelution temperature for several comparable ethylene/1-octeneinterpolymers (random copolymers) are fit to a line representing(−0.2013)T+20.07 (solid line). The line for the equation(−0.2013)T+21.07 is depicted by a dotted line. Also depicted are thecomonomer contents for fractions of several block ethylene/1-octeneinterpolymers of the invention (multi-block copolymers). All of theblock interpolymer fractions have significantly higher 1-octene contentthan either line at equivalent elution temperatures. This result ischaracteristic of the inventive interpolymer and is believed to be dueto the presence of differentiated blocks within the polymer chains,having both crystalline and amorphous nature.

FIG. 5 graphically displays the TREF curve and comonomer contents ofpolymer fractions for Example 5 and Comparative Example F* to bediscussed below. The peak eluting from 40 to 130° C., preferably from60° C. to 95° C. for both polymers is fractionated into three parts,each part eluting over a temperature range of less than 10° C. Actualdata for Example 5 is represented by triangles. The skilled artisan canappreciate that an appropriate calibration curve may be constructed forinterpolymers containing different comonomers and a line used as acomparison fitted to the TREF values obtained from comparativeinterpolymers of the same monomers, preferably random copolymers madeusing a metallocene or other homogeneous catalyst composition. Inventiveinterpolymers are characterized by a molar comonomer content greaterthan the value determined from the calibration curve at the same TREFelution temperature, preferably at least 5 percent greater, morepreferably at least 10 percent greater.

In addition to the above aspects and properties described herein, theinventive polymers can be characterized by one or more additionalcharacteristics. In one aspect, the inventive polymer is an olefininterpolymer, preferably comprising ethylene and one or morecopolymerizable comonomers in polymerized form, characterized bymultiple blocks or segments of two or more polymerized monomer unitsdiffering in chemical or physical properties (blocked interpolymer),most preferably a multi-block copolymer, said block interpolymer havinga molecular fraction which elutes between 40° C. and 130° C., whenfractionated using TREF increments, characterized in that said fractionhas a molar comonomer content higher, preferably at least 5 percenthigher, more preferably at least 10, 15, 20 or 25 percent higher, thanthat of a comparable random ethylene interpolymer fraction elutingbetween the same temperatures, wherein said comparable random ethyleneinterpolymer comprises the same comonomer(s), preferably it is the samecomonomer(s), and a melt index, density, and molar comonomer content(based on the whole polymer) within 10 percent of that of the blockedinterpolymer. Preferably, the Mw/Mn of the comparable interpolymer isalso within 10 percent of that of the blocked interpolymer and/or thecomparable interpolymer has a total comonomer content within 10 weightpercent of that of the blocked interpolymer.

Preferably, the above interpolymers are interpolymers of ethylene and atleast one α-olefin, especially those interpolymers having a wholepolymer density from about 0.855 to about 0.935 g/cm³, and moreespecially for polymers having more than about 1 mole percent comonomer,the blocked interpolymer has a comonomer content of the TREF fractioneluting between 40 and 130° C. greater than or equal to the quantity(−0.1356)T+13.89, more preferably greater than or equal to the quantity(−0.1356)T+14.93, and most preferably greater than or equal to thequantity (−0.2013)T+21.07, where T is the numerical value of the peakATREF elution temperature of the TREF fraction being compared, measuredin ° C.

Preferably, for the above interpolymers of ethylene and at least onealpha-olefin especially those interpolymers having a whole polymerdensity from about 0.855 to about 0.935 g/cm³, and more especially forpolymers having more than about 1 mole percent comonomer, the blockedinterpolymer has a comonomer content of the TREF fraction elutingbetween 40 and 130° C. greater than or equal to the quantity(−0.2013)T+20.07, more preferably greater than or equal to the quantity(−0.2013)T+21.07, where T is the numerical value of the peak elutiontemperature of the TREF fraction being compared, measured in ° C.

In still another aspect, the inventive polymer is an olefininterpolymer, preferably comprising ethylene and one or morecopolymerizable comonomers in polymerized form, characterized bymultiple blocks or segments of two or more polymerized monomer unitsdiffering in chemical or physical properties (blocked interpolymer),most preferably a multi-block copolymer, said block interpolymer havinga molecular fraction which elutes between 40° C. and 130° C., whenfractionated using TREF increments, characterized in that every fractionhaving a comonomer content of at least about 6 mole percent has amelting point greater than about 100° C. For those fractions having acomonomer content from about 3 mole percent to about 6 mole percent,every fraction has a DSC melting point of about 110° C. or higher. Morepreferably, said polymer fractions, having at least I mol percentcomonomer, has a DSC melting point that corresponds to the equation:Tm≧(−5.5926)(mol percent comonomer in the fraction)+135.90.

In yet another aspect, the inventive polymer is an olefin interpolymer,preferably comprising ethylene and one or more copolymerizablecomonomers in polymerized form, characterized by multiple blocks orsegments of two or more polymerized monomer units differing in chemicalor physical properties (blocked interpolymer), most preferably amulti-block copolymer, said block interpolymer having a molecularfraction which elutes between 40° C. and 130° C., when fractionatedusing TREF increments, characterized in that every fraction that has anATREF elution temperature greater than or equal to about 76° C., has amelt enthalpy (heat of fusion) as measured by DSC, corresponding to theequation:Heat of fusion (J/gm)≦(3.1718)(ATREF elution temperature inCelsius)−136.58,

The inventive block interpolymers have a molecular fraction which elutesbetween 40° C. and 130° C., when fractionated using TREF increments,characterized in that every fraction that has an ATREF elutiontemperature between 40° C. and less than about 76° C., has a meltenthalpy (heat of fusion) as measured by DSC, corresponding to theequation:Heat of fusion (J/gm)≦(1.1312)(ATREF elution temperature inCelsius)+22.97.ATREF Peak Comonomer Composition Measurement by Infra-Red Detector

The comonomer composition of the TREF peak can be measured using an IR4infra-red detector available from Polymer Char, Valencia, Spain(http://www.polymerchar.com/).

The “composition mode” of the detector is equipped with a measurementsensor (CH₂) and composition sensor (CH₃) that are fixed narrow bandinfra-red filters in the region of 2800-3000 cm⁻¹. The measurementsensor detects the methylene (CH₂) carbons on the polymer (whichdirectly relates to the polymer concentration in solution) while thecomposition sensor detects the methyl (CH₃) groups of the polymer. Themathematical ratio of the composition signal (CH₃) divided by themeasurement signal (CH₂) is sensitive to the comonomer content of themeasured polymer in solution and its response is calibrated with knownethylene alpha-olefin copolymer standards.

The detector when used with an ATREF instrument provides both aconcentration (CH₂) and composition (CH₃) signal response of the elutedpolymer during the TREF process. A polymer specific calibration can becreated by measuring the area ratio of the CH₃ to CH₂ for polymers withknown comonomer content (preferably measured by NMR). The comonomercontent of an ATREF peak of a polymer can be estimated by applying a thereference calibration of the ratio of the areas for the individual CH₃and CH₂ response (i.e. area ratio CH₃/CH₂ versus comonomer content).

The area of the peaks can be calculated using a full width/half maximum(FWHM) calculation after applying the appropriate baselines to integratethe individual signal responses from the TREF chromatogram. The fullwidth/half maximum calculation is based on the ratio of methyl tomethylene response area [CH₃/CH₂] from the ATREF infra-red detector,wherein the tallest (highest) peak is identified from the base line, andthen the FWHM area is determined. For a distribution measured using anATREF peak, the FWHM area is defined as the area under the curve betweenT1 and T2, where T1 and T2 are points determined, to the left and rightof the ATREF peak, by dividing the peak height by two, and then drawinga line horizontal to the base line, that intersects the left and rightportions of the ATREF curve.

The application of infra-red spectroscopy to measure the comonomercontent of polymers in this ATREF-infra-red method is, in principle,similar to that of GPC/FTIR systems as described in the followingreferences: Markovich, Ronald P.; Hazlitt, Lonnie G.; Smith, Linley;“Development of gel-permeation chromatography-Fourier transform infraredspectroscopy for characterization of ethylene-based polyolefincopolymers”. Polymeric Materials Science and Engineering (1991), 65,98-100.; and Deslauriers, P. J.; Rohlfing, D. C.; Shieh, E. T.;“Quantifying short chain branching microstructures in ethylene-1-olefincopolymers using size exclusion chromatography and Fourier transforminfrared spectroscopy (SEC-FTIR)”, Polymer (2002), 43, 59-170., both ofwhich are incorporated by reference herein in their entirety.

In other embodiments, the inventive ethylene/α-olefin interpolymer ischaracterized by an average block index, ABI, which is greater than zeroand up to about 1.0 and a molecular weight distribution, M_(w)/M_(n),greater than about 1.3. The average block index, ABI, is the weightaverage of the block index (“BI”) for each of the polymer fractionsobtained in preparative TREF from 20° C. and 110° C., with an incrementof 5° C.:ABI=Σ(w _(i) BI _(i))where BI_(i) is the block index for the ith fraction of the inventiveethylene/α-olefin interpolymer obtained in preparative TREF, and w_(i)is the weight percentage of the ith fraction.

For each polymer fraction, BI is defined by one of the two followingequations (both of which give the same BI value):${BI} = {{\frac{{1/T_{X}} - {1/T_{XO}}}{{1/T_{A}} - {1/T_{AB}}}\quad{or}{\quad\quad}{BI}} = {- \frac{{LnP}_{X} - {LnP}_{XO}}{{LnP}_{A} - {LnP}_{AB}}}}$where T_(X) is the preparative ATREF elution temperature for the ithfraction (preferably expressed in Kelvin), P_(X) is the ethylene molefraction for the ith fraction, which can be measured by NMR or IR asdescribed above. P_(AB) is the ethylene mole fraction of the wholeethylene/α-olefin interpolymer (before fractionation), which also can bemeasured by NMR or IR. T_(A) and P_(A) are the ATREF elution temperatureand the ethylene mole fraction 30 for pure “hard segments” (which referto the crystalline segments of the interpolymer). As a first orderapproximation, the T_(A) and P_(A) values are set to those for highdensity polyethylene homopolymer, if the actual values for the “hardsegments” are not available. For calculations performed herein, T_(A) is372° K, P_(A) is 1.

T_(AB) is the ATREF temperature for a random copolymer of the samecomposition and having an ethylene mole fraction of P_(AB). T_(AB) canbe calculated from the following equation:Ln P _(AB) =α/T _(AB)+βwhere α and β are two constants which can be determined by calibrationusing a number of known random ethylene copolymers. It should be notedthat α and β may vary from instrument to instrument. Moreover, one wouldneed to create their own calibration lo curve with the polymercomposition of interest and also in a similar molecular weight range asthe fractions. There is a slight molecular weight effect. If thecalibration curve is obtained from similar molecular weight ranges, sucheffect would be essentially negligible. In some embodiments, randomethylene copolymers satisfy the following relationship:Ln P=−237.83/T _(ATREF)+0.639

T_(XO) is the ATREF temperature for a random copolymer of the samecomposition and having an ethylene mole fraction of P_(X). T_(XO) can becalculated from LnP_(X)=α/T_(XO)+β. Conversely, P_(XO) is the ethylenemole fraction for a random copolymer of the same composition and havingan ATREF temperature of T_(X), which can be calculated from LnP_(XO)=α/T_(X)+β.

Once the block index (BI) for each preparative TREF fraction isobtained, the weight average block index, ABI, for the whole polymer canbe calculated. In some embodiments, ABI is greater than zero but lessthan about 0.3 or from about 0.1 to about 0.3. In other embodiments, ABIis greater than about 0.3 and up to about 1.0. Preferably, ABI should bein the range of from about 0.4 to about 0.7, from about 0.5 to about0.7, or from about 0.6 to about 0.9. In some embodiments, ABI is in therange of from about 0.3 to about 0.9, from about 0.3 to about 0.8, orfrom about 0.3 to about 0.7, from about 0.3 to about 0.6, from about 0.3to about 0.5, or from about 0.3 to about 0.4. In other embodiments, ABIis in the range of from about 0.4 to about 1.0, from about 0.5 to about1.0, or from about 0.6 to about 1.0, from about 0.7 to about 1.0, fromabout 0.8 to about 1.0, or from about 0.9 to about 1.0.

Another characteristic of the inventive ethylene/α-olefin interpolymeris that the inventive ethylene/α-olefin interpolymer comprises at leastone polymer fraction which can be obtained by preparative TREF, whereinthe fraction has a block index greater than about 0.1 and up to about1.0 and a molecular weight distribution, M_(w)/M_(n), greater than about1.3. In some embodiments, the polymer fraction has a block index greaterthan about 0.6 and up to about 1.0, greater than about 0.7 and up toabout 1.0, greater than about 0.8 and up to about 1.0, or greater thanabout 0.9 and up to about 1.0. In other embodiments, the polymerfraction has a block index greater than about 0.1 and up to about 1.0,greater than about 0.2 and up to about 1.0, greater than about 0.3 andup to about 1.0, greater than about 0.4 and up to about 1.0, or greaterthan about 0.4 and up to about 1.0. In still other embodiments, thepolymer fraction has a block index greater than about 0.1 and up toabout 0.5, greater than about 0.2 and up to about 0.5, greater thanabout 0.3 and up to about 0.5, or greater than about 0.4 and up to about0.5. In yet other embodiments, the polymer fraction has a block indexgreater than about 0.2 and up to about 0.9, greater than about 0.3 andup to about 0.8, greater than about 0.4 and up to about 0.7, or greaterthan about 0.5 and up to about 0.6.

For copolymers of ethylene and an α-olefin, the inventive polymerspreferably possess (1) a PDI of at least 1.3, more preferably at least1.5, at least 1.7, or at least 2.0, and most preferably at least 2.6, upto a maximum value of 5.0, more preferably up to a maximum of 3.5, andespecially up to a maximum of 2.7; (2) a heat of fusion of 80 J/g orless; (3) an ethylene content of at least 50 weight percent; (4) a glasstransition temperature, T_(g), of less than −25° C., more preferablyless than −30° C., and/or (5) one and only one T_(m).

Further, the inventive polymers can have, alone or in combination withany other properties disclosed herein, a storage modulus, G′, such thatlog (G′) is greater than or equal to 400 kPa, preferably greater than orequal to 1.0 MPa, at a temperature of 100° C. Moreover, the inventivepolymers possess a relatively flat storage modulus as a function oftemperature in the range from 0 to 100° C. (illustrated in FIG. 6) thatis characteristic of block copolymers, and heretofore unknown for anolefin copolymer, especially a copolymer of ethylene and one or moreC₃₋₈ aliphatic α-olefins. (By the term “relatively flat” in this contextis meant that log G′ (in Pascals) decreases by less than one order ofmagnitude between 50 and 100° C., preferably between 0 and 100° C.).

The inventive interpolymers may be further characterized by athermomechanical analysis penetration depth of I mm at a temperature ofat least 90° C. as well as a flexural modulus of from 3 kpsi (20 MPa) to13 kpsi (90 MPa). Alternatively, the inventive interpolymers can have athermomechanical analysis penetration depth of 1 mm at a temperature ofat least 104° C. as well as a flexural modulus of at least 3 kpsi (20MPa). They may be characterized as having an abrasion resistance (orvolume loss) of less than 90 mm³. FIG. 7 shows the TMA (1 mm) versusflex modulus for the inventive polymers, as compared to other knownpolymers. The inventive polymers have significantly betterflexibility-heat resistance balance than the other polymers.

Additionally, the ethylene/α-olefin interpolymers can have a melt index,I₂, from 0.01 to 2000 g/10 minutes, preferably from 0.01 to 1000 g/10minutes, more preferably from 0.01 to 500 g/10 minutes, and especiallyfrom 0.01 to 100 g/10 minutes. In certain embodiments, theethylene/α-olefin interpolymers have a melt index, I₂, from 0.01 to 10 g10 minutes, from 0.5 to 50 g/10 minutes, from I to 30 g/10 minutes, from1 to 6 g/10 minutes or from 0.3 to 10 g/10 minutes. In certainembodiments, the melt index for the ethylene/α-olefin polymers is 1 g/10minutes, 3 g/10 minutes or 5 g/10 minutes.

The polymers can have molecular weights, M_(w), from 1,000 g/mole to5,000,000 g/mole, preferably from 1000 g/mole to 1,000,000, morepreferably from 10,000 g/mole to 500,000 g/mole, and especially from10,000 g/mole to 300,000 g/mole. The density of the inventive polymerscan be from 0.80 to 0.99 g/cm³ and preferably for ethylene containingpolymers from 0.85 g/cm³ to 0.97 g/cm³. In certain embodiments, thedensity of the ethylene/α-olefin polymers ranges from 0.860 to 0.925g/cm³ or 0.867 to 0.910 g/cm³.

The process of making the polymers has been disclosed in the followingpatent applications: U.S. Provisional Application No. 60/553,906, filedMar. 17, 2004; U.S. Provisional Application No. 60/662,937, filed Mar.17, 2005; U.S. Provisional Application No. 60/662,939, filed Mar. 17,2005; U.S. Provisional Application No. 60/5662938, filed Mar. 17, 2005;PCT Application No. PCT/US2005/008916, filed Mar. 17, 2005; PCTApplication No. PCT/US2005/008915, filed Mar. 17, 2005; and PCTApplication No. PCT/US2005/008917, filed Mar. 17, 2005, all of which areincorporated by reference herein in their entirety. For example, onesuch method comprises contacting ethylene and optionally one or moreaddition polymerizable monomers other than ethylene under additionpolymerization conditions with a catalyst composition comprising:

the admixture or reaction product resulting from combining:

(A) a first olefin polymerization catalyst having a high comonomerincorporation index,

(B) a second olefin polymerization catalyst having a comonomerincorporation index less than 90 percent, preferably less than 50percent, most preferably less than 5 percent of the comonomerincorporation index of catalyst (A), and

(C) a chain shuttling agent.

Representative catalysts and chain shuttling agent are as follows.

Catalyst (A1) is[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl, prepared according to the teachings of WO 03/40195, 2003U.S.Pat. No. 0,204,017, U.S. Ser. No. 10/429,024, filed May 2, 2003, and WO04/24740.

Catalyst (A2) is[N-(2,6-di(1-methylethyl)phenyl)amido)(2-methylphenyl)(1,2-phenylene-(6-pyridin-2-diyl)methane)]hafniumdimethyl, prepared according to the teachings of WO 03/40195, 2003U.S.Pat. No. 0,204,017, U.S. Ser. No. 10/429,024, filed May 2, 2003, and WO04/24740.

Catalyst (A3) isbis[N,N′″-(2,4,6-tri(methylphenyl)amido)ethylenediamine]hafniumdibenzyl.

Catalyst (A4) isbis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)cyclohexane-1,2-diylzirconium (IV) dibenzyl, prepared substantially to the teachings ofUS-A-2004/0010103.

Catalyst (B1) is1,2-bis-(3,5-di-t-butylphenylene)(1-(N-(1-methylethyl)immino)methyl)(2-oxoyl)zirconiumdibenzyl

Catalyst (B2) is1,2-bis-(3,5-di-t-butylphenylene)(1-(N-(2-methylcyclohexyl)-immino)methyl)(2-oxoyl)zirconiumdibenzyl

Catalyst (C1) is(t-butylamido)dimethyl(3-N-pyrrolyl-1,2,3,3a,7a-η-inden-1-yl)silanetitaniumdimethyl prepared substantially according to the techniques of U.S. Pat.No. 6,268,444:

Catalyst (C2) is(t-butylamido)di(4-methylphenyl)(2-methyl-1,2,3,3a,7a-η-inden-1-yl)silanetitaniumdimethyl prepared substantially according to the teachings ofUS-A-2003/004286:

Catalyst (C3) is(t-butylamido)di(4-methylphenyl)(2-methyl-1,2,3,3a,8a-η-s-indacen-1-yl)silanetitaniumdimethyl prepared substantially according to the teachings ofUS-A-2003/004286:

Catalyst (D1) is bis(dimethyldisiloxane)(indene-1-yl)zirconiumdichloride available from Sigma-Aldrich:

Shuttling Agents The shuttling agents employed include diethylzinc,di(i-butyl)zinc, di(n-hexyl)zinc, triethylaluminum, trioctylaluminum,triethylgallium, i-butylaluminum bis(dimethyl(t-butyl)siloxane),i-butylaluminum bis(di(trimethylsilyl)amide), n-octylaluminumdi(pyridine-2-methoxide), bis(n-octadecyl)i-butylaluminum,i-butylaluminum bis(di(n-pentyl)amide), n-octylaluminumbis(2,6-di-t-butylphenoxide, n-octylaluminum di(ethyl(1-naphthyl)amide),ethylaluminum bis(t-butyldimethylsiloxide), ethylaluminumdi(bis(trimethylsilyl)amide), ethylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide), n-octylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide), n-octylaluminumbis(dimethyl(t-butyl)siloxide, ethylzinc (2,6-diphenylphenoxide), andethylzinc (t-butoxide).

Preferably, the foregoing process takes the form of a continuoussolution process for forming block copolymers, especially multi-blockcopolymers, preferably linear multi-block copolymers of two or moremonomers, more especially ethylene and a C₃₋₂₀ olefin or cycloolefin,and most especially ethylene and a C₄₋₂₀ α-olefin, using multiplecatalysts that are incapable of interconversion. That is, the catalystsare chemically distinct. Under continuous solution polymerizationconditions, the process is ideally suited for polymerization of mixturesof monomers at high monomer conversions. Under these polymerizationconditions, shuttling from the chain shuttling agent to the catalystbecomes advantaged compared to chain growth, and multi-block copolymers,especially linear multi-block copolymers are formed in high efficiency.

The inventive interpolymers may be differentiated from conventional,random copolymers, physical blends of polymers, and block copolymersprepared via sequential monomer addition, fluxional catalysts, anionicor cationic living polymerization techniques. In particular, compared toa random copolymer of the same monomers and monomer content atequivalent crystallinity or modulus, the inventive interpolymers havebetter (higher) heat resistance as measured by melting point, higher TMApenetration temperature, higher high-temperature tensile strength,and/or higher high-temperature torsion storage modulus as determined bydynamic mechanical analysis. Compared to a random copolymer containingthe same monomers and monomer content, the inventive interpolymers havelower compression set, particularly at elevated temperatures, lowerstress relaxation, higher creep resistance, higher tear strength, higherblocking resistance, faster setup due to higher crystallization(solidification) temperature, higher recovery (particularly at elevatedtemperatures), better abrasion resistance, higher retractive force, andbetter oil and filler acceptance.

The inventive interpolymers also exhibit a unique crystallization andbranching distribution relationship. That is, the inventiveinterpolymers have a relatively large difference between the tallestpeak temperature measured using CRYSTAF and DSC as a function of heat offusion, especially as compared to random copolymers containing the samemonomers and monomer level or physical blends of polymers, such as ablend of a high density polymer and a lower density copolymer, atequivalent overall density. It is believed that this unique feature ofthe inventive interpolymers is due to the unique distribution of thecomonomer in blocks within the polymer backbone. In particular, theinventive interpolymers may comprise alternating blocks of differingcomonomer content (including homopolymer blocks). The inventiveinterpolymers may also comprise a distribution in number and/or blocksize of polymer blocks of differing density or comonomer content, whichis a Schultz-Flory type of distribution. In addition, the inventiveinterpolymers also have a unique peak melting point and crystallizationtemperature profile that is substantially independent of polymerdensity, modulus, and morphology. In a preferred embodiment, themicrocrystalline order of the polymers demonstrates characteristicspherulites and lamellae that are distinguishable from random or blockcopolymers, even at PDI values that are less than 1.7, or even less than1.5, down to less than 1.3.

Moreover, the inventive interpolymers may be prepared using techniquesto influence the degree or level of blockiness. That is the amount ofcomonomer and length of each polymer block or segment can be altered bycontrolling the ratio and type of catalysts and shuttling agent as wellas the temperature of the polymerization, and other polymerizationvariables. A surprising benefit of this phenomenon is the discovery thatas the degree of blockiness is increased, the optical properties, tearstrength, and high temperature recovery properties of the resultingpolymer are improved. In particular, haze decreases while clarity, tearstrength, and high temperature recovery properties increase as theaverage number of blocks in the polymer increases. By selectingshuttling agents and catalyst combinations having the desired chaintransferring ability (high rates of shuttling with low levels of chaintermination) other forms of polymer termination are effectivelysuppressed. Accordingly, little if any β-hydride elimination is observedin the polymerization of ethylene/α-olefin comonomer mixtures accordingto embodiments of the invention, and the resulting crystalline blocksare highly, or substantially completely, linear, possessing little or nolong chain branching.

Polymers with highly crystalline chain ends can be selectively preparedin accordance with embodiments of the invention. In elastomerapplications, reducing the relative quantity of polymer that terminateswith an amorphous block reduces the intermolecular dilutive effect oncrystalline regions. This result can be obtained by choosing chainshuttling agents and catalysts having an appropriate response tohydrogen or other chain terminating agents. Specifically, if thecatalyst which produces highly crystalline polymer is more susceptibleto chain termination (such as by use of hydrogen) than the catalystresponsible for producing the less crystalline polymer segment (such asthrough higher comonomer incorporation, regio-error, or atactic polymerformation), then the highly crystalline polymer segments willpreferentially populate the terminal portions of the polymer. Not onlyare the resulting terminated groups crystalline, but upon termination,the highly crystalline polymer forming catalyst site is once againavailable for reinitiation of polymer formation. The initially formedpolymer is therefore another highly crystalline polymer segment.Accordingly, both ends of the resulting multi-block copolymer arepreferentially highly crystalline.

The ethylene α-olefin interpolymers used in the embodiments of theinvention are preferably interpolymers of ethylene with at least oneC₃-C₂₀ α-olefin. Copolymers of ethylene and a C₃-C₂₀ α-olefin areespecially preferred. The interpolymers may further comprise C₄-C₁₈diolefin and/or alkenylbenzene. Suitable unsaturated comonomers usefulfor polymerizing with ethylene include, for example, ethylenicallyunsaturated monomers, conjugated or nonconjugated dienes, polyenes,alkenylbenzenes, etc. Examples of such comonomers include C₃-C₂₀α-olefins such as propylene, isobutylene, 1-butene, 1-hexene, 1-pentene,4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, and thelike. 1-Butene and 1-octene are especially preferred. Other suitablemonomers include styrene, halo- or alkyl-substituted styrenes,vinylbenzocyclobutane, 1,4-hexadiene, 1,7-octadiene, and naphthenics(e.g., cyclopentene, cyclohexene and cyclooctene).

While ethylene/α-olefin interpolymers are preferred polymers, otherethylene/olefin polymers may also be used. Olefins as used herein referto a family of unsaturated hydrocarbon-based compounds with at least onecarbon-carbon double bond. Depending on the selection of catalysts, anyolefin may be used in embodiments of the invention. Preferably, suitableolefins are C₃-C₂₀ aliphatic and aromatic compounds containing vinylicunsaturation, as well as cyclic compounds, such as cyclobutene,cyclopentene, dicyclopentadiene, and norbornene, including but notlimited to, norbornene substituted in the 5 and 6 position with C₁-C₂₀hydrocarbyl or cyclohydrocarbyl groups. Also included are mixtures ofsuch olefins as well as mixtures of such olefins with C₄-C₄₀ diolefincompounds.

Examples of olefin monomers include, but are not limited to propylene,isobutylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene,1-nonene, 1-decene, and 1-dodecene, 1-tetradecene, 1-hexadecene,1-octadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene,4-methyl-1-pentene, 4,6-dimethyl-1-heptene, 4-vinylcyclohexene,vinylcyclohexane, norbornadiene, ethylidene norbornene, cyclopentene,cyclohexene, dicyclopentadiene, cyclooctene, C₄-C₄₀ dienes, includingbut not limited to 1,3-butadiene, 1,3-pentadiene, 1,4-hexadiene,1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, other C₄-C₄₀ α-olefins, andthe like. In certain embodiments, the α-olefin is propylene, 1-butene,1-pentene, 1-hexene, 1-octene or a combination thereof. Although anyhydrocarbon containing a vinyl group potentially may be used inembodiments of the invention, practical issues such as monomeravailability, cost, and the ability to conveniently remove unreactedmonomer from the resulting polymer may become more problematic as themolecular weight of the monomer becomes too high.

The polymerization processes described herein are well suited for theproduction of olefin polymers comprising monovinylidene aromaticmonomers including styrene, o-methyl styrene, p-methyl styrene,t-butylstyrene, and the like. In particular, interpolymers comprisingethylene and styrene can be prepared by following the teachings herein.Optionally, copolymers comprising ethylene, styrene and a C₃-C₂₀ alphaolefin, optionally comprising a C₄-C₂₀ diene, having improved propertiescan be prepared.

Suitable non-conjugated diene monomers can be a straight chain, branchedchain or cyclic hydrocarbon diene having from 6 to 15 carbon atoms.Examples of suitable non-conjugated dienes include, but are not limitedto, straight chain acyclic dienes, such as 1,4-hexadiene, 1,6-octadiene,1,7-octadiene, 1,9-decadiene, branched chain acyclic dienes, such as5-methyl-1,4-hexadiene; 3,7-dimethyl-1,6-octadiene;3,7-dimethyl-1,7-octadiene and mixed isomers of dihydromyricene anddihydroocinene, single ring alicyclic dienes, such as1,3-cyclopentadiene; 1,4-cyclohexadiene; 1,5-cyclooctadiene and1,5-cyclododecadiene, and multi-ring alicyclic fused and bridged ringdienes, such as tetrahydroindene, methyl tetrahydroindene,dicyclopentadiene, bicyclo-(2,2,1)-hepta-2,5-diene; alkenyl, alkylidene,cycloalkenyl and cycloalkylidene norbornenes, such as5-methylene-2-norbornene (MNB); 5-propenyl-2-norbornene,5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene,5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene, and norbornadiene.Of the dienes typically used to prepare EPDMs, the particularlypreferred dienes are 1,4-hexadiene (HD), 5-ethylidene-2-norbornene(ENB), 5-vinylidene-2-norbornene (VNB), 5-methylene-2-norbornene (MNB),and dicyclopentadiene (DCPD). The especially preferred dienes are5-ethylidene-2-norbornene (ENB) and 1,4-hexadiene (HD).

One class of desirable polymers that can be made in accordance withembodiments of the invention are elastomeric interpolymers of ethylene,a C₃-C₂₀ α-olefin, especially propylene, and optionally one or morediene monomers. Preferred α-olefins for use in this embodiment of thepresent invention are designated by the formula CH₂═CHR*, where R* is alinear or branched alkyl group of from 1 to 12 carbon atoms. Examples ofsuitable α-olefins include, but are not limited to, propylene,isobutylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and1-octene. A particularly preferred α-olefin is propylene. The propylenebased polymers are generally referred to in the art as EP or EPDMpolymers. Suitable dienes for use in preparing such polymers, especiallymulti-block EPDM type polymers include conjugated or non-conjugated,straight or branched chain-, cyclic- or polycyclic-dienes comprisingfrom 4 to 20 carbons. Preferred dienes include 1,4-pentadiene,1,4-hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene,cyclohexadiene, and 5-butylidene-2-norbornene. A particularly preferreddiene is 5-ethylidene-2-norbornene.

Because the diene containing polymers comprise alternating segments orblocks containing greater or lesser quantities of the diene (includingnone) and α-olefin (including none), the total quantity of diene andα-olefin may be reduced without loss of subsequent polymer properties.That is, because the diene and α-olefin monomers are preferentiallyincorporated into one type of block of the polymer rather than uniformlyor randomly throughout the polymer, they are more efficiently utilizedand subsequently the crosslink density of the polymer can be bettercontrolled. Such crosslinkable elastomers and the cured products haveadvantaged properties, including higher tensile strength and betterelastic recovery.

In some embodiments, the inventive interpolymers made with two catalystsincorporating differing quantities of comonomer have a weight ratio ofblocks formed thereby from 95:5 to 5:95. The elastomeric polymersdesirably have an ethylene content of from 20 to 90 percent, a dienecontent of from 0.1 to 10 percent, and an α-olefin content of from 10 to80 percent, based on the total weight of the polymer. Furtherpreferably, the multi-block elastomeric polymers have an ethylenecontent of from 60 to 90 percent, a diene content of from 0.1 to 10percent, and an α-olefin content of from 10 to 40 percent, based on thetotal weight of the polymer. Preferred polymers are high molecularweight polymers, having a weight average molecular weight (Mw) from10,000 to about 2,500,000, preferably from 20,000 to 500,000, morepreferably from 20,000 to 350,000, and a polydispersity less than 3.5,more preferably less than 3.0, and a Mooney viscosity (ML (1+4) 125° C.)from 1 to 250. More preferably, such polymers have an ethylene contentfrom 65 to 75 percent, a diene content from 0 to 6 percent, and anα-olefin content from 20 to 35 percent.

The ethylene/α-olefin interpolymers can be functionalized byincorporating at least one functional group in its polymer structure.Exemplary functional groups may include, for example, ethylenicallyunsaturated mono- and di-functional carboxylic acids, ethylenicallyunsaturated mono- and di-functional carboxylic acid anhydrides, saltsthereof and esters thereof. Such functional groups may be grafted to anethylene/α-olefin interpolymer, or it may be copolymerized with ethyleneand an optional additional comonomer to form an interpolymer ofethylene, the functional comonomer and optionally other comonomer(s).Means for grafting functional groups onto polyethylene are described forexample in U.S. Pat. Nos. 4,762,890, 4,927,888, and 4,950,541, thedisclosures of these patents are incorporated herein by reference intheir entirety. One particularly useful functional group is malicanhydride.

The amount of the functional group present in the functionalinterpolymer can vary. The functional group can typically be present ina copolymer-type functionalized interpolymer in an amount of at leastabout 1.0 weight percent, preferably at least about 5 weight percent,and more preferably at least about 7 weight percent. The functionalgroup will typically be present in a copolymer-type functionalizedinterpolymer in an amount less than about 40 weight percent, preferablyless than about 30 weight percent, and more preferably less than about25 weight percent.

The amount of the ethylene/α-olefin interpolymer in the polymer blendsdisclosed herein depends upon several factors, such as the type andamount of the two polyolefins. Generally, the amount should besufficient to be effective as a compatibilizer as decribed above. Insome embodiments, it should be an a sufficient amount to effectmorphology changes between the two polymers in the resulting blend.Typically the amount can be from about 0.5 to about 99 wt %, from about5 to about 95 wt %, from about 10 to about 90 wt %, from about 20 toabout 80 wt %, from about 0.5 to about 50 wt %, from about 50 to about99 wt %, from about 5 to about 50 wt %, or from about 50 to about 95 wt% of the total weight of the polymer blend. In some embodiments, theamount of the ethylene/α-olefin interpolymer in the polymer blends isfrom about 1% to about 30%, from about 2% to about 20%, from about 3% toabout 15%, from about 4% to about 10% by weight of the total weight ofthe polymer blend. In some embodiments, the amount of theethylene/α-olefin interpolymer in the polymer blends is less than about50%, less than about 40%, less than about 30%, less than about 20%, lessthan about 15%, less than about 10%, less than about 9%, less than about8%, less than about 7%, less than about 6%, less than about 5%, lessthan about 4%, less than about 3%, less than about 2% or less than about1%, but greater than about 0.1% by weight of the total polymer blend.

Polyolefins

The polymer blends disclosed herein can comprise at least twopolyoelfins, in addition to at least an ethylene/α-olefin interpolymerdescribed above. A polyolefin is a polymer derived from two or moreolefins (i.e., alkenes). An olefin (i.e., alkene) is a hydrocarboncontains at least one carbon-carbon double bond. The olefin can be amonoene (i.e, an olefin having a single carbon-carbon double bond),diene (i.e, an olefin having two carbon-carbon double bonds), triene(i.e, an olefin having three carbon-carbon double bonds), tetraene (i.e,an olefin having four carbon-carbon double bonds), and other polyenes.The olefin or alkene, such as monoene, diene, triene, tetraene and otherpolyenes, can have 3 or more carbon atoms, 4 or more carbon atoms, 6 ormore carbon atoms, 8 or more carbon atoms. In some embodiments, theolefin has from 3 to about 100 carbon atoms, from 4 to about 100 carbonatoms, from 6 to about 100 carbon atoms, from 8 to about 100 carbonatoms, from 3 to about 50 carbon atoms, from 3 to about 25 carbon atoms,from 4 to about 25 carbon atoms, from 6 to about 25 carbon atoms, from 8to about 25 carbon atoms, or from 3 to about 10 carbon atoms. In someembodiments, the olefin is a linear or branched, cyclic or acyclic,monoene having from 2 to about 20 carbon atoms. In other embodiments,the alkene is a diene such as butadiene and 1,5-hexadiene. In furtherembodiments, at least one of the hydrogen atoms of the alkene issubstituted with an alkyl or aryl. In particular embodiments, the alkeneis ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene,4-methyl-1-pentene, norbornene, 1-decene, butadiene, 1,5-hexadiene,styrene or a combination thereof.

The amount of the polyolefins in the polymer blend can be from about 0.5to about 99 wt %, from about 10 to about 90 wt %, from about 20 to about80 wt %, from about 30 to about 70 wt %, from about 5 to about 50 wt %,from about 50 to about 95 wt %, from about 10 to about 50 wt %, or fromabout 50 to about 90 wt % of the total weight of the polymer blend. Inone embodiment, the amount of the polyolefins in the polymer blend isabout 50%, 60%, 70% or 80% by total weight of the polymer blend. Theweight ratio of the two polyolefins can range from about 1:99 to about99:1, preferable from about 5:95 to about 95:5, from about 10:90 toabout 90: 10, from about 20:80 to about 80:20, from about 30:70 to about70:30, from about 40:60 to about 60:40, from about 45:55 to about 55:45to about 50:50.

Any polyolefin known to a person of ordinary skill in the art may beused to prepare the polymer blend disclosed herein. The polyolefins canbe olefin homopolymers, olefin copolymers, olefin terpolymers, olefinquaterpolymers and the like, and combinations thereof.

In some embodiments, one of the at least two polyolefins is an olefinhomopolymer. The olefin homopolymer can be derived from one olefin. Anyolefin homopolymer known to a person of ordinary skill in the art may beused. Non-limiting examples of olefin homopolymers include polyethylene(e.g., ultralow, low, linear low, medium, high and ultrahigh densitypolyethylene), polypropylene, polybutylene (e.g., polybutene-1),polypentene-1, polyhexene-1, polyoctene-1, polydecene-1,poly-3-methylbutene-1, poly-4-methylpentene-1, polyisoprene,polybutadiene, poly-1,5-hexadiene.

In further embodiments, the olefin homopolymer is a polypropylene. Anypolypropylene known to a person of ordinary skill in the art may be usedto prepare the polymer blends disclosed herein. Non-limiting examples ofpolypropylene include low density polypropylene (LDPP), high densitypolypropylene (HDPP), high melt strength polypropylene (HMS-PP), highimpact polypropylene (HIPP), isotactic polypropylene (iPP), syndiotacticpolypropylene (sPP) and the like, and combinations thereof.

The amount of the polypropylene in the polymer blend can be from about0.5 to about 99 wt %, from about 10 to about 90 wt %, from about 20 toabout 80 wt %, from about 30 to about 70 wt %, from about 5 to about 50wt %, from about 50 to about 95 wt %, from about 10 to about 50 wt %, orfrom about 50 to about 90 wt % of the total weight of the polymer blend.In one embodiment, the amount of the polypropylene in the polymer blendis about 50%, 60%, 70% or 80% by total weight of the polymer blend.

In other embodiments, one of the at least two polyolefins is an olefincopolymer. The olefin copolymer can be derived from two differentolefins. The amount of the olefin copolymer in the polymer blend can befrom about 0.5 to about 99 wt %, from about 10 to about 90 wt %, fromabout 20 to about 80 wt %, from about 30 to about 70 wt %, from about 5to about 50 wt %, from about 50 to about 95 wt %, from about 10 to about50 wt %, or from about 50 to about 90 wt % of the total weight of thepolymer blend. In some embodiments, the amount of the olefin copolymerin the polymer blend is about 10%, 15%, 20%, 25%, 30%, 35%, 40% or 50%of the total weight of the polymer blend.

Any olefin copolymer known to a person of ordinary skill in the art maybe used in the polymer blends disclosed herein. Non-limiting examples ofolefin copolymers include copolymers derived from ethylene and a monoenehaving 3 or more carbon atoms. Non-limiting examples of the monoenehaving 3 or more carbon atoms include propene; butenes (e.g., 1-butene,2-butene and isobutene) and allyl substituted butenes; pentenes (e.g.,1-pentene and 2-pentene) and alkyl substituted pentenes (e.g.,4-methyl-1-pentene); hexenes (e.g., 1-hexene, 2-hexene and 3-hexene) andalkyl substituted hexenes; heptenes (e.g., 1-heptene, 2-heptene and3-heptene) and alkyl substituted heptenes; octenes (e.g., 1-octene,2-octene, 3-octene and 4-octene) and alkyl substituted octenes; nonenes(e.g., 1-nonene, 2-nonene, 3-nonene and 4-nonene) and alkyl substitutednonenes; decenes (e.g., 1-decene, 2-decene, 3-decene, 4-decene and5-decene) and alkyl substituted decenes; dodecenes and alkyl substituteddodecenes; and butadiene. In some embodiments, the olefin copolymer isan ethylene/alpha-olefin (EAO) copolymer or ethylene/propylene copolymer(EPM). In some embodiments, the olefin copolymer is an ethylene/octenecopolymer.

In other embodiments, the olefin copolymer is derived from (i) a C₃₋₂₀olefin substituted with an alkyl or aryl group (e.g., 4-methyl-1-penteneand styrene) and (ii) a diene (e.g. butadiene, 1,5-hexadiene,1,7-octadiene and 1,9-decadiene). A non-limiting example of such olefincopolymer includes styrene-butadiene-styrene (SBS) block copolymer.

In other embodiments, one of the at least two polyolefins is an olefinterpolymer. The olefin terpolymer can be derived from three differentolefins. The amount of the olefin terpolymer in the polymer blend can befrom about 0.5 to about 99 wt %, from about 10 to about 90 wt %, fromabout 20 to about 80 wt %, from about 30 to about 70 wt %, from about 5to about 50 wt %, from about 50 to about 95 wt %, from about 10 to about50 wt %, or from about 50 to about 90 wt % of the total weight of thepolymer blend.

Any olefin terpolymer known to a person of ordinary skill in the art maybe used in the polymer blends disclosed herein. Non-limiting examples ofolefin terpolymers include terpolymers derived from (i) ethylene, (ii) amonoene having 3 or more carbon atoms, and (iii) a diene. In someembodiments, the olefin terpolymer is an ethylene/alpha-olefin/dieneterpolymers (EAODM) and ethylene/propylene/diene terpolymer (EPDM).

In other embodiments, the olefin terpolymer is derived from (i) twodifferent monoenes, and (ii) a C₃₋₂₀ olefin substituted with an alkyl oraryl group. A non-limiting example of such olefin terpolymer includesstyrene-ethylene-co-(butene)-styrene (SEBS) block copolymer.

In other embodiments, one of the at least two polyolefins can be anyvulcanizable elastomer or rubber which is derived from at least anolefin, provided that the vulcanizable elastomer can be cross-linked(i.e., vulcanized) by a cross-linking agent. The vulcanizable elastomerand a thermoplastic such as polypropylene together can form a TPV aftercross-linking. Vulcanizable elastomers, although generally thermoplasticin the uncured state, are normally classified as thermosets because theyundergo an irreversible process of thermosetting to an unprocessablestate. Preferably, the vulcanized elastomer is dispersed in a matrix ofthe thermoplastic polymer as domains. The average domain size may rangefrom about 0.1 micron to about 100 micron, from about 1 micron to about50 microns; from about 1 micron to about 25 microns; from about 1 micronto about 10 microns, or from about 1 micron to about 5 microns.

Non-limiting examples of suitable vulcanizable elastomers or rubbersinclude ethylene/higher alpha-olefin/polyene terpolymer rubbers such asEPDM. Any such terpolymer rubber which can be completely cured(cross-linked) with a phenolic curative or other cross-linking agent issatisfactory. In some embodiments, the terpolymer rubbers can beessentially non-crystalline, rubbery terpolymer of two or morealpha-olefins, preferably copolymerized with at least one polyene (i.e,an alkene comprises two or more carbon-carbon double bonds), usually anon-conjugated diene. Suitable terpolymer rubbers comprise the productsfrom the polymerization of monomers comprising two olefins having onlyone double bond, generally ethylene and propylene, and a lesser quantityof non-conjugated diene. The amount of non-conjugated diene is usuallyfrom about 2 to about 10 weight percent of the rubber. Any terpolymerrubber which has sufficient reactivity with phenolic curative tocompletely cure is suitable. The reactivity of terpolymer rubber variesdepending upon both the amount of unsaturation and the type ofunsaturation present in the polymer. For example, terpolymer rubbersderived from ethylidene norbornene are more reactive toward phenoliccuratives than terpolymer rubbers derived from dicyclopentadiene andterpolymer rubbers derived from 1,4-hexadiene are less reactive towardphenolic curatives than terpolymer rubbers derived fromdicyclopentadiene. However, the differences in reactivity can beovercome by polymerizing larger quantities of less active diene into therubber molecule. For example, 2.5 weight percent of ethylidenenorbornene or dicyclopentadiene may be sufficient to impart sufficientreactivity to the terpolymer to make it completely curable with phenoliccurative comprising conventional cure activators, whereas, at least 3.0weight percent or more is required to obtain sufficient reactivity in anterpolymer rubber derived from 1,4-hexadiene. Grades of terpolymerrubbers such as EPDM rubbers suitable for embodiments of the inventionare commercially available. Some of the EPDM rubbers are disclosed inRubber World Blue Book 1975 Edition, Materials and CompoundingIngredients for Rubber, pages 406-410.

Generally, an terpolymer elastomer has an ethylene content of from about10% to about 90% by weight, a higher alpha-olefin content of about 10%to about 80% by weight, and a polyene content of about 0.5% to about 20%by weight, all weights based on the total weight of the polymer. Thehigher alpha-olefin contains from about 3 to about 14 carbon atoms.Examples of these are propylene, isobutylene, 1-butene, 1-pentene,1-octene, 2-ethyl-1-hexene, 1-dodecene, and the like. The polyene can bea conjugated diene such as isoprene, butadiene, chloroprene, and thelike; a nonconjugated diene; a triene, or a higher enumerated polyene.Examples of trienes are 1,4,9-decatriene, 5,8-dimethyl-1,4,9-decatriene,4,9-dimethyl-1,4,9-decatriene, and the like. The nonconjugated dienesare more preferred. The nonconjugated dienes contain from 5 to about 25carbon atoms. Examples are nonconjugated diolefins such as1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene,2,5-dimethyl-1,5-hexadiene, 1,4-octadiene, and the like; cyclic dienessuch as cyclopentadiene, cyclohexadiene, cyclooctadiene,dicyclopentadiene, and the like; vinyl cyclic enes such as1-vinyl-1-cyclopentene, 1-vinyl-1-cyclohexene, and the like;alkylbicyclo nondienes such as 3-methyl-bicyclo (4,2,1)nona-3,7-diene,3-ethylbicyclonondiene, and the like; indenes such as methyltetrahydroindene and the like; alkenyl norbornenes such as5-ethylidene-2-norbornene, 5-butylidene-2-norbornene,2-methallyl-5-norbornene, 2-isopropenyl-5-norbornene,5-(1,5-hexadienyl)-2-norbornene, 5-(3,7-octadieneyl)-2-norbornene, andthe like; and tricyclo dienes such as3-methyl-tricyclo-(5,2,1,0²,6)-3,8-decadiene and the like.

In some embodiments, the terpolymer rubbers contain from about 20% toabout 80% by weight of ethylene, about 19% to about 70% by weight of ahigher alpha-olefin, and about 1% to about 10% by weight of anonconjugated diene. The more preferred higher alpha-olefins arepropylene and 1-butene. The more preferred polyenes are ethylidenenorbornene, 1,4-hexadiene, and dicyclopentadiene.

In other embodiments, the terpolymer rubbers have an ethylene content offrom about 50% to about 70% by weight, a propylene content of from about20% to about 49% by weight, and a nonconjugated diene content from about1% to about 10% by weight, all weights based upon the total weight ofthe polymer.

Some non-limiting examples of terpolymer rubbers for use include NORDEL®IP 4770R, NORDEL® 3722 IP available from DuPont Dow Elastomers,Wilmington, Del. and KELTAN® 5636A available from DSM ElastomersAmericas, Addis, La.

Additional suitable elastomers are disclosed in the following U.S. Pat.Nos. 4,130,535; 4,111,897; 4,311,628; 4,594,390; 4,645,793; 4,808,643;4,894,408; 5,936,038, 5,985,970; and 6,277,916, all of which areincorporated by reference herein in their entirety.

Additives

Optionally, the polymer blends disclosed herein can comprise at leastone additive for the purposes of improving and/or controlling theprocessibility, appearance, physical, chemical, and/or mechanicalproperties of the polymer blends. In some embodiments, the polymerblends do not comprise an additive. Any plastics additive known to aperson of ordinary skill in the art may be used in the polymer blendsdisclosed herein. Non-limiting examples of suitable additives includeslip agents, anti-blocking agents, plasticizers, antioxidants, UVstabilizers, colorants or pigments, fillers, lubricants, antifoggingagents, flow aids, coupling agents, cross-linking agents, nucleatingagents, surfactants, solvents, flame retardants, antistatic agents, andcombinations thereof. The total amount of the additives can range fromabout greater than 0 to about 80%, from about 0.001% to about 70%, fromabout 0.01% to about 60%, from about 0.1% to about 50%, from about 1% toabout 40%, or from about 10% to about 50% of the total weight of thepolymer blend. Some polymer additives have been described in ZweifelHans et al., “Plastics Additives Handbook,” Hanser Gardner Publications,Cincinnati, Ohio, 5th edition (2001), which is incorporated herein byreference in its entirety.

In some embodiments, the polymer blends disclosed herein comprise a slipagent. In other embodiments, the polymer blends disclosed herein do notcomprise a slip agent. Slip is the sliding of film surfaces over eachother or over some other substrates. The slip performance of films canbe measured by ASTM D 1894, Static and Kinetic Coefficients of Frictionof Plastic Film and Sheeting, which is incorporated herein by reference.In general, the slip agent can convey slip properties by modifying thesurface properties of films; and reducing the friction between layers ofthe films and between the films and other surfaces with which they comeinto contact.

Any slip agent known to a person of ordinary skill in the art may beadded to the polymer blends disclosed herein. Non-limiting examples ofthe slip agents include primary amides having about 12 to about 40carbon atoms (e.g., erucamide, oleamide, stearamide and behenamide);secondary amides having about 18 to about 80 carbon atoms (e.g., stearylerucamide, behenyl erucamide, methyl erucamide and ethyl erucamide);secondary-bis-amides having about 18 to about 80 carbon atoms (e.g.,ethylene-bis-stearamide and ethylene-bis-oleamide); and combinationsthereof. In a particular embodiment, the slip agent for the polymerblends disclosed herein is an amide represented by Formula (I) below:

wherein each of R¹ and R² is independently H, alkyl, cycloalkyl,alkenyl, cycloalkenyl or aryl; and R³ is alkyl or alkenyl, each havingabout 11 to about 39 carbon atoms, about 13 to about 37 carbon atoms,about 15 to about 35 carbon atoms, about 17 to about 33 carbon atoms orabout 19 to about 33 carbon atoms. In some embodiments, R³ is alkyl oralkenyl, each having at least 19 to about 39 carbon atoms. In otherembodiments, R³ is pentadecyl, heptadecyl, nonadecyl, heneicosanyl,tricosanyl, pentacosanyl, heptacosanyl, nonacosanyl, hentriacontanyl,tritriacontanyl, nonatriacontanyl or a combination thereof. In furtherembodiments, R³ is pentadecenyl, heptadecenyl, nonadecenyl,heneicosanenyl, tricosanenyl, pentacosanenyl, heptacosanenyl,nonacosanenyl, hentriacontanenyl, tritriacontanenyl, nonatriacontanenylor a combination thereof.

In some embodiments, the slip agent is a primary amide with a saturatedaliphatic group having between 18 and about 40 carbon atoms (e.g.,stearamide and behenamide). In other embodiments, the slip agent is aprimary amide with an unsaturated aliphatic group containing at leastone carbon-carbon double bond and between 18 and about 40 carbon atoms(e.g., erucamide and oleamide). In further embodiments, the slip agentis a primary amide having at least 20 carbon atoms. In furtherembodiments, the slip agent is erucamide, oleamide, stearamide,behenamide, ethylene-bis-stearamide, ethylene-bis-oleamide, stearylerucamide, behenyl erucamide or a combination thereof. In a particularembodiment, the slip agent is erucamide. In further embodiments, theslip agent is commercially available having a trade name such as ATMER™SA from Uniqema, Everberg, Belgium; ARMOSLIP® from Akzo Nobel PolymerChemicals, Chicago, Ill.; KEMAMIDE® from Witco, Greenwich, Conn.; andCRODAMIDE® from Croda, Edison, N.J. Where used, the amount of the slipagent in the polymer blend can be from about greater than 0 to about 3wt %, from about 0.0001 to about 2 wt %, from about 0.001 to about I wt%, from about 0.001 to about 0.5 wt % or from about 0.05 to about 0.25wt % of the total weight of the polymer blend. Some slip agents havebeen described in Zweifel Hans et al., “Plastics Additives Handbook,”Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 8,pages 601-608 (2001), which is incorporated herein by reference.

Optionally, the polymer blends disclosed herein can comprise ananti-blocking agent. In some embodiments, the polymer blends disclosedherein do not comprise an anti-blocking agent. The anti-blocking agentcan be used to prevent the undesirable adhesion between touching layersof articles made from the polymer blends, particularly under moderatepressure and heat during storage, manufacture or use. Any anti-blockingagent known to a person of ordinary skill in the art may be added to thepolymer blends disclosed herein. Non-limiting examples of anti-blockingagents include minerals (e.g., clays, chalk, and calcium carbonate),synthetic silica gel (e.g., SYLOBLOC® from Grace Davison, Columbia,Md.), natural silica (e.g., SUPER FLOSS® from Celite Corporation, SantaBarbara, Calif.), talc (e.g., OPTIBLOC®O from Luzenac, Centennial,Colo.), zeolites (e.g., SIPERNAT® from Degussa, Parsippany, N.J.),aluminosilicates (e.g., SILTON® from Mizusawa Industrial Chemicals,Tokyo, Japan), limestone (e.g., CARBOREX® from Omya, Atlanta, Ga.),spherical polymeric particles (e.g., EPOSTAR®, poly(methyl methacrylate)particles from Nippon Shokubai, Tokyo, Japan and TOSPEARL®, siliconeparticles from GE Silicones, Wilton, Conn.), waxes, amides (e.g.erucamide, oleamide, stearamide, behenamide, ethylene-bis-stearamide,ethylene-bis-oleamide, stearyl erucamide and other slip agents),molecular sieves, and combinations thereof. The mineral particles canlower blocking by creating a physical gap between articles, while theorganic anti-blocking agents can migrate to the surface to limit surfaceadhesion. Where used, the amount of the anti-blocking agent in thepolymer blend can be from about greater than 0 to about 3 wt %, fromabout 0.0001 to about 2 wt %, from about 0.001 to about 1 wt %, or fromabout 0.001 to about 0.5 wt % of the total weight of the polymer blend.Some anti-blocking agents have been described in Zweifel Hans et al.,“Plastics Additives Handbook,” Hanser Gardner Publications, Cincinnati,Ohio, 5th edition, Chapter 7, pages 585-600 (2001), which isincorporated herein by reference.

Optionally, the polymer blends disclosed herein can comprise aplasticizer. In general, a plasticizer is a chemical that can increasethe flexibility and lower the glass transition temperature of polymers.Any plasticizer known to a person of ordinary skill in the art may beadded to the polymer blends disclosed herein. Non-limiting examples ofplasticizers include abietates, adipates, alkyl sulfonates, azelates,benzoates, chlorinated paraffins, citrates, epoxides, glycol ethers andtheir esters, glutarates, hydrocarbon oils, isobutyrates, oleates,pentaerythritol derivatives, phosphates, phthalates, esters,polybutenes, ricinoleates, sebacates, sulfonamides, tri- andpyromellitates, biphenyl derivatives, stearates, difuran diesters,fluorine-containing plasticizers, hydroxybenzoic acid esters, isocyanateadducts, multi-ring aromatic compounds, natural product derivatives,nitriles, siloxane-based plasticizers, tar-based products, thioeters andcombinations thereof. Where used, the amount of the plasticizer in thepolymer blend can be from greater than 0 to about 15 wt %, from about0.5 to about 10 wt %, or from about 1 to about 5 wt % of the totalweight of the polymer blend. Some plasticizers have been described inGeorge Wypych, “Handbook of Plasticizers,” ChemTec Publishing,Toronto-Scarborough, Ontario (2004), which is incorporated herein byreference.

In some embodiments, the polymer blends disclosed herein optionallycomprise an antioxidant that can prevent the oxidation of polymercomponents and organic additives in the polymer blends. Any antioxidantknown to a person of ordinary skill in the art may be added to thepolymer blends disclosed herein. Non-limiting examples of suitableantioxidants include aromatic or hindered amines such as alkyldiphenylamines, phenyl-α-naphthylamine, alkyl or aralkyl substitutedphenyl-a-naphthylamine, alkylated p-phenylene diamines,tetramethyl-diaminodiphenylamine and the like; phenols such as2,6-di-t-butyl-4-methylphenol;1,3,5-trimethyl-2,4,6-tris(3′,5′-di-t-butyl-4′-hydroxybenzyl)benzene;tetrakis[(methylene(3,5-di-t-butyl-4-hydroxyhydrocinnamate)]methane(e.g., IRGANOX™ 1010, from Ciba Geigy, New York); acryloyl modifiedphenols; octadecyl-3,5-di-t-butyl-4-hydroxycinnamate (e.g., IRGANOX™1076, commercially available from Ciba Geigy); phosphites andphosphonites; hydroxylamines; benzofuranone derivatives; andcombinations thereof. Where used, the amount of the antioxidant in thepolymer blend can be from about greater than 0 to about 5 wt %, fromabout 0.0001 to about 2.5 wt %, from about 0.001 to about 1 wt %, orfrom about 0.001 to about 0.5 wt % of the total weight of the polymerblend. Some antioxidants have been described in Zweifel Hans et al.,“Plastics Additives Handbook,” Hanser Gardner Publications, Cincinnati,Ohio, 5th edition, Chapter 1, pages 1-140 (2001), which is incorporatedherein by reference.

In other embodiments, the polymer blends disclosed herein optionallycomprise an UV stabilizer that may prevent or reduce the degradation ofthe polymer blends by UV radiations. Any UV stabilizer known to a personof ordinary skill in the art may be added to the polymer blendsdisclosed herein. Non-limiting examples of suitable UV stabilizersinclude benzophenones, benzotriazoles, aryl esters, oxanilides, acrylicesters, formamidines, carbon black, hindered amines, nickel quenchers,hindered amines, phenolic antioxidants, metallic salts, zinc compoundsand combinations thereof. Where used, the amount of the UV stabilizer inthe polymer blend can be from about greater than 0 to about 5 wt %, fromabout 0.01 to about 3 wt %, from about 0.1 to about 2 wt %, or fromabout 0.1 to about I wt % of the total weight of the polymer blend. SomeUV stabilizers have been described in Zweifel Hans et al., “PlasticsAdditives Handbook,” Hanser Gardner Publications, Cincinnati, Ohio, 5thedition, Chapter 2, pages 141-426 (2001), which is incorporated hereinby reference.

In further embodiments, the polymer blends disclosed herein optionallycomprise a colorant or pigment that can change the look of the polymerblends to human eyes. Any colorant or pigment known to a person ofordinary skill in the art may be added to the polymer blends disclosedherein. Non-limiting examples of suitable colorants or pigments includeinorganic pigments such as metal oxides such as iron oxide, zinc oxide,and titanium dioxide, mixed metal oxides, carbon black, organic pigmentssuch as anthraquinones, anthanthrones, azo and monoazo compounds,arylamides, benzimidazolones, BONA lakes, diketopyrrolo-pyrroles,dioxazines, disazo compounds, diarylide compounds, flavanthrones,indanthrones, isoindolinones, isoindolines, metal complexes, monoazosalts, naphthols, b-naphthols, naphthol AS, naphthol lakes, perylenes,perinones, phthalocyanines, pyranthrones, quinacridones, andquinophthalones, and combinations thereof. Where used, the amount of thecolorant or pigment in the polymer blend can be from about greater than0 to about 10 wt %, from about 0.1 to about 5 wt %, or from about 0.25to about 2 wt % of the total weight of the polymer blend. Some colorantshave been described in Zweifel Hans et al., “Plastics AdditivesHandbook,” Hanser Gardner Publications, Cincinnati, Ohio, 5th edition,Chapter 15, pages 813-882 (2001), which is incorporated herein byreference.

Optionally, the polymer blends disclosed herein can comprise a fillerwhich can be used to adjust, inter alia, volume, weight, costs, and/ortechnical performance. Any filler known to a person of ordinary skill inthe art may be added to the polymer blends disclosed herein.Non-limiting examples of suitable fillers include talc, calciumcarbonate, chalk, calcium sulfate, clay, kaolin, silica, glass, fumedsilica, mica, wollastonite, feldspar, aluminum silicate, calciumsilicate, alumina, hydrated alumina such as alumina trihydrate, glassmicrosphere, ceramic microsphere, thermoplastic microsphere, barite,wood flour, glass fibers, carbon fibers, marble dust, cement dust,magnesium oxide, magnesium hydroxide, antimony oxide, zinc oxide, bariumsulfate, titanium dioxide, titanates and combinations thereof. In someembodiments, the filler is barium sulfate, talc, calcium carbonate,silica, glass, glass fiber, alumina, titanium dioxide, or a mixturethereof. In other embodiments, the filler is talc, calcium carbonate,barium sulfate, glass fiber or a mixture thereof. Where used, the amountof the filler in the polymer blend can be from about greater than 0 toabout 80 wt %, from about 0.1 to about 60 wt %, from about 0.5 to about40 wt %, from about 1 to about 30 wt %, or from about 10 to about 40 wt% of the total weight of the polymer blend. Some fillers have beendisclosed in U.S. Pat. No. 6,103,803 and Zweifel Hans et al., “PlasticsAdditives Handbook,” Hanser Gardner Publications, Cincinnati, Ohio, 5thedition, Chapter 17, pages 901-948 (2001), both of which areincorporated herein by reference.

Optionally, the polymer blends disclosed herein can comprise alubricant. In general, the lubricant can be used, inter alia, to modifythe rheology of the molten polymer blends, to improve the surface finishof molded articles, and/or to facilitate the dispersion of fillers orpigments. Any lubricant known to a person of ordinary skill in the artmay be added to the polymer blends disclosed herein. Non-limitingexamples of suitable lubricants include fatty alcohols and theirdicarboxylic acid esters, fatty acid esters of short-chain alcohols,fatty acids, fatty acid amides, metal soaps, oligomeric fatty acidesters, fatty acid esters of long-chain alcohols, montan waxes,polyethylene waxes, polypropylene waxes, natural and synthetic paraffinwaxes, fluoropolymers and combinations thereof. Where used, the amountof the lubricant in the polymer blend can be from about greater than 0to about 5 wt %, from about 0.1 to about 4 wt %, or from about 0.1 toabout 3 wt % of the total weight of the polymer blend. Some suitablelubricants have been disclosed in Zweifel Hans et al., “PlasticsAdditives Handbook,” Hanser Gardner Publications, Cincinnati, Ohio, 5thedition, Chapter 5, pages 511-552 (2001), both of which are incorporatedherein by reference.

Optionally, the polymer blends disclosed herein can comprise anantistatic agent. Generally, the antistatic agent can increase theconductivity of the polymer blends and to prevent static chargeaccumulation. Any antistatic agent known to a person of ordinary skillin the art may be added to the polymer blends disclosed herein.Non-limiting examples of suitable antistatic agents include conductivefillers (e.g., carbon black, metal particles and other conductiveparticles), fatty acid esters (e.g., glycerol monostearate), ethoxylatedalkylamines, diethanolamides, ethoxylated alcohols, alkylsulfonates,alkylphosphates, quaternary ammonium salts, alkylbetaines andcombinations thereof. Where used, the amount of the antistatic agent inthe polymer blend can be from about greater than 0 to about 5 wt %, fromabout 0.01 to about 3 wt %, or from about 0.1 to about 2 wt % of thetotal weight of the polymer blend. Some suitable antistatic agents havebeen disclosed in Zweifel Hans et al., “Plastics Additives Handbook,”Hanser Gardner Publications, Cincinnati, Ohio, 5th edition, Chapter 10,pages 627-646 (2001), both of which are incorporated herein byreference.

In further embodiments, the polymer blends disclosed herein optionallycomprise a cross-linking agent that can be used to increase thecross-linking density of the polymer blends. Any cross-linking agentknown to a person of ordinary skill in the art may be added to thepolymer blends disclosed herein. Non-limiting examples of suitablecross-linking agents include organic peroxides (e.g., alkyl peroxides,aryl peroxides, peroxyesters, peroxycarbonates, diacylperoxides,peroxyketals, and cyclic peroxides) and silanes (e.g.,vinyltrimethoxysilane, vinyltriethoxysilane,vinyltris(2-methoxyethoxy)silane, vinyltriacetoxysilane,vinylmethyldimethoxysilane, and3-methacryloyloxypropyltrimethoxysilane). Where used, the amount of thecross-linking agent in the polymer blend can be from about greater than0 to about 20 wt %, from about 0.1 to about 15 wt %, or from about 1 toabout 10 wt % of the total weight of the polymer blend. Some suitablecross-linking agents have been disclosed in Zweifel Hans et al.,“Plastics Additives Handbook,” Hanser Gardner Publications, Cincinnati,Ohio, 5th edition, Chapter 14, pages 725-812 (2001), both of which areincorporated herein by reference.

The cross-linking of the polymer blends can also be initiated by anyradiation means known in the art, including, but not limited to,electron-beam irradiation, beta irradiation, gamma irradiation, coronairradiation, and UV radiation with or without cross-linking catalyst.U.S. patent application Ser. No. 10/086,057 (published as US2002/0132923A1) and U.S. Pat. No. 6,803,014 disclose electron-beam irradiationmethods that can be used in embodiments of the invention.

Preparation of the Polymer blends

The ingredients of the polymer blends, i.e., the ethylene/α-olefininterpolymer, the polyolefins (i.e., the first polyolefin and the secondpolyolefin) and the optional additives, can be mixed or blended usingmethods known to a person of ordinary skill in the art, preferablymethods that can provide a substantially homogeneous distribution of thepolyolefin and/or the additives in the ethylene/α-olefin interpolymer.Non-limiting examples of suitable blending methods include meltblending, solvent blending, extruding, and the like.

In some embodiments, the ingredients of the polymer blends are meltblended by a method as described by Guerin et al. in U.S. Pat. No.4,152,189. First, all solvents, if there are any, are removed from theingredients by heating to an appropriate elevated temperature of about100C to about 200° C. or about 150° C. to about 175° C. at a pressure ofabout 5 torr (667 Pa) to about 10 torr (1333 Pa). Next, the ingredientsare weighed into a vessel in the desired proportions and the polymerblend is formed by heating the contents of the vessel to a molten statewhile stirring.

In other embodiments, the ingredients of the polymer blends areprocessed using solvent blending. First, the ingredients of the desiredpolymer blend are dissolved in a suitable solvent and the mixture isthen mixed or blended. Next, the solvent is removed to provide thepolymer blend.

In further embodiments, physical blending devices that providedispersive mixing, distributive mixing, or a combination of dispersiveand distributive mixing can be useful in preparing homogenous blends.Both batch and continuous methods of physical blending can be used.Non-limiting examples of batch methods include those methods usingBRABENDER(® mixing equipments (e.g., BRABENDER PREP CENTER®, availablefrom C. W. Brabender Instruments, Inc., South Hackensack, N.J.) orBANBURY® internal mixing and roll milling (available from FarrelCompany, Ansonia, Conn.) equipment. Non-limiting examples of continuousmethods include single screw extruding, twin screw extruding, diskextruding, reciprocating single screw extruding, and pin barrel singlescrew extruding. In some embodiments, the additives can be added into anextruder through a feed hopper or feed throat during the extrusion ofthe ethylene/α-olefin interpolymer, the polyolefin or the polymer blend.The mixing or blending of polymers by extrusion has been described in C.Rauwendaal, “Polymer Extrusion”, Hanser Publishers, New York, N.Y.,pages 322-334 (1986), which is incorporated herein by reference.

When one or more additives are required in the polymer blends, thedesired amounts of the additives can be added in one charge or multiplecharges to the ethylene/α-olefin interpolymer, the polyolefins or thepolymer blend. Furthermore, the addition can take place in any order. Insome embodiments, the additives are first added and mixed or blendedwith the ethylene/α-olefin interpolymer and then the additive-containinginterpolymer is blended with the polyolefins. In other embodiments, theadditives are first added and mixed or blended with the polyolefins andthen with the ethylene/α-olefin interpolymer. In further embodiments,the ethylene/α-olefin interpolymer is blended with the polyolefins firstand then the additives are blended with the polymer blend.

Alternatively, master batches containing high concentrations of theadditives can be used. In general, master batches can be prepared byblending either the ethylene/α-olefin interpolymer, one of thepolyolefins or the polymer blend with high concentrations of additives.The master batches can have additive concentrations from about I toabout 50 wt %, from about 1 to about 40 wt %, from about 1 to about 30wt %, or from about 1 to about 20 wt % of the total weight of thepolymer blend. The master batches can then be added to the polymerblends in an amount determined to provide the desired additiveconcentrations in the end products. In some embodiments, the masterbatch contains a slip agent, an anti-blocking agent, a plasticizer, anantioxidant, a UV stabilizer, a colorant or pigment, a filler, alubricant, an antifogging agent, a flow aid, a coupling agent, across-linking agent, a nucleating agent, a surfactant, a solvent, aflame retardant, an antistatic agent, or a combination thereof. In otherembodiment, the master batch contains a slip agent, an anti-blockingagent or a combination thereof. In other embodiment, the master batchcontains a slip agent.

In some embodiments, the first polyolefin and the second polyolefintogether constitute a thermoplastic vulcanizate where the firstpolyolefin is a thermoplastic such as polypropylene and the secondpolyolefin is a curable vulcanizable rubber such as EPDM. Thethermoplastic vulcanizates are typically prepared by blending thethermoplastic and curable vulcanizable rubber by dynamic vulcanization.The compositions can be prepared by any suitable method for mixing ofrubbery polymers including mixing on a rubber mill or in internal mixerssuch as a Banbury mixer. In the compounding procedure, one or moreadditives as described above can be incorporated. Generally, it ispreferred to add the cross-linking or curing agents in a second stage ofcompounding which may be on a rubber mill or in an internal mixeroperated at a temperature normally not in excess of about 60° C.

Dynamic vulcanization is a process whereby a blend of thermoplastic,rubber and rubber curative is masticated while curing the rubber. Theterm “dynamic” indicates the mixture is subjected to shear forces duringthe vulcanization step as contrasted with “static” vulcanization whereinthe vulcanizable composition is immobile (in fixed relative space)during the vulcanization step. One advantage of dynamic vulcanization isthat elastoplastic (thermoplastic elastomeric) compositions may beobtained when the blend contains the proper proportions of plastic andrubber. Examples of dynamic vulcanization are described in U.S. Pat.Nos. 3,037,954; 3,806,558; 4,104,210; 4,116,914; 4,130,535; 4,141,863;4,141,878; 4,173,556; 4,207,404; 4,271,049 4,287,324; 4,288,570;4,299,931; 4,311,628 and 4,338,413, all of which are incorporated hereinby reference in their entirety.

Any mixer capable of generating a shear rate of 2000 sect⁻¹ or higher issuitable for carrying out the process. Generally, this requires a highspeed internal mixer having a narrow clearance between the tips of thekneading elements and the wall. Shear rate is the velocity gradient inthe space between the tip and the wall. Depending upon the clearancebetween the tip and the wall, rotation of the kneading elements fromabout 100 to about 500 revolutions per minute (rpm) is generallyadequate to develop a sufficient shear rate. Depending upon the numberof tips on a given kneading element and the rate of rotation, the numberof times the composition is kneaded by each element is from about 1 toabout 30 times per second, preferably from about 5 to about 30 times persecond, and more preferably from about 10 to about 30 times per second.This means that material typically is kneaded from about 200 to about1800 times during vulcanization. For example, in a typical process witha rotor with three tips rotating at about 400 rpm in a mixer having aresidence time of about 30 seconds, the material is kneaded about 600times.

A mixer satisfactory for carrying out the process is a high shear mixingextruder produced by Werner & Pfleiderer, Germany. The Werner &Pfleiderer (W&P) extruder is a twin-shaft screw extruder in which twointermeshing screws rotate in the same direction. Details of suchextruders are described in U.S. Pat. Nos. 3,963,679 and 4,250,292; andGerman Pat. Nos. 2,302,546; 2,473,764 and 2,549,372, the disclosures ofwhich are incorporated herein by reference. Screw diameters vary fromabout 53 mm to about 300 mm; barrel lengths vary but generally themaximum barrel length is the length necessary to maintain a length overdiameter ratio of about 42. The shaft screws of these extruders normallyare made-up of alternating series of conveying sections and kneadingsections. The conveying sections cause material to move forward fromeach kneading section of the extruder. Typically there are about anequal number of conveying and kneading sections fairly evenlydistributed along the length of the barrel. Kneading elements containingone, two, three or four tips are suitable, however, kneading elementsfrom about 5 to about 30 mm wide having three tips are preferred. Atrecommended screw speeds of from about 100 to about 600 rpm and radialclearance of from about 0.1 to about 0.4 mm, these mixing extrudersprovide shear rates of at least from about 2000 sec⁻¹ to about 7500sec⁻¹ or more. The net mixing power expended in the process includinghomogenization and dynamic vulcanization is usually from about 100 toabout 500 watt hours per kilogram of product produced; with from about300 to about 400 watt hours per kilogram being typical.

The process is illustrated by the use of W&P twin screw extruders,models ZSK-53 or ZSK-83. Unless specified otherwise, all of the plastic,rubber and other compounding ingredients except the cure activator arefed into the entry port of the extruder. In the first third of theextruder, the composition is masticated to melt the plastic and to forman essentially homogeneous blend. The cure activator (vulcanizationaccelerator) is added through another entry port located about one-thirdof the length of the barrel downstream from the initial entry port. Thelast two-thirds of the extruder (from the cure activator entry port tothe outlet of the extruder) is regarded as the dynamic vulcanizationzone. A vent operated under reduced pressure is located near the outletto remove any volatile by-products. Sometimes, additional extender oilor plasticizer and colorants are added at another entry port locatedabout the middle of the vulcanization zone.

The residence time within the vulcanization zone is the time a givenquantity of material is within the aforesaid vulcanization zone. Sincethe extruders are typically operated under a starved condition, usuallyfrom about 60 to about 80 percent full, residence time is essentiallydirectly proportional to feed rate. Thus, residence time in thevulcanization zone is calculated by multiplying the total volume of thedynamic vulcanization zone times the fill factor divided by the volumeflow rate. Shear rate is calculated by dividing the product of thecircumference of the circle generated by the screw tip times therevolutions of the screw per second by the tip clearance. In otherwords, shear rate is the tip velocity divided by the tip clearance.

Methods other than the dynamic curing of rubber/thermoplastic polymerresin blends can be utilized to prepare compositions. For example, therubber can be fully cured in the absence of the thermoplastic polymerresin, either dynamically or statically, powdered, and mixed with thethermoplastic polymer resin at a temperature above the melting orsoftening point of the resin. If the cross-linked rubber particles aresmall, well dispersed and in an appropriate concentration, thecompositions are easily obtained by blending cross-linked rubber andthermoplastic polymer resin. It is preferred that a mixture comprisingwell dispersed small particles of cross-linked rubber is obtained. Amixture which contains poor dispersed or too large rubber particles canbe comminuted by cold milling, to reduce particle size to below about 50μl, preferably below about 20 μl and more preferably to below about 5 μ.After sufficient comminution or pulverization, a TPV composition isobtained. Frequently, poor dispersion or too large rubber particles isobvious to the naked eye and observable in a molded sheet. This isespecially true in the absence of pigments and fillers. In such a case,pulverization and remolding gives a sheet in which aggregates of rubberparticles or large particles are not obvious or are far less obvious tothe naked eye and mechanical properties are greatly improved.

Applications of the Polymer Blends

The polymer blends disclosed herein are useful for making a variety ofarticles such as tires, hoses, belts, gaskets, shoe soles, moldings andmolded parts. They are particularly useful for applications that requirehigh melt strength such as large part blow molding, foams, and wirecables. Additional applications are disclosed in the following U.S. Pat.Nos. 6,329,463; 6,288,171; 6,277,916; 6,270,896; 6,221,451; 6,174,962;6,169,145; 6,150,464; 6,147,160; 6,100,334; 6,084,031; 6,069,202;6,066,697; 6,028,137; 6,020,427; 5,977,271; 5,960,977; 5,957,164;5,952,425; 5,939,464; 5,936,038; 5,869,591; 5,750,625; 5,744,238;5,621,045; and 4,783,579, all of which are incorporated herein byreference in their entirety.

The polymer blends can be used to prepare various useful articles withknown polymer processes such as extrusion (e.g., sheet extrusion andprofile extrusion), injection molding, molding, rotational molding, andblow molding. In general, extrusion is a process by which a polymer ispropelled continuously along a screw through regions of high temperatureand pressure where it is melted and compacted, and finally forcedthrough a die. The extruder can be a single screw extruder, a multiplescrew extruder, a disk extruder or a ram extruder. The die can be a filmdie, blown film die, sheet die, pipe die, tubing die or profileextrusion die. The extrusion of polymers has been described in C.Rauwendaal, “Polymer Extrusion”, Hanser Publishers, New York, N.Y.(1986); and M. J. Stevens, “Extruder Principals and Operation,”Ellsevier Applied Science Publishers, New York, N.Y. (1985), both ofwhich are incorporated herein by reference in their entirety.

Injection molding is also widely used for manufacturing a variety ofplastic parts for various applications. In general, injection molding isa process by which a polymer is melted and injected at high pressureinto a mold, which is the inverse of the desired shape, to form parts ofthe desired shape and size. The mold can be made from metal, such assteel and aluminum. The injection molding of polymers has been describedin Beaumont et al., “Successful Injection Molding: Process, Design, andSimulation,” Hanser Gardner Publications, Cincinnati, Ohio (2002), whichis incorporated herein by reference in its entirety.

Molding is generally a process by which a polymer is melted and led intoa mold, which is the inverse of the desired shape, to form parts of thedesired shape and size. Molding can be pressureless orpressure-assisted. The molding of polymers is described in Hans-GeorgElias “An Introduction to Plastics,” Wiley-VCH, Weinhei, Germany, pp.161-165 (2003), which is incorporated herein by reference.

Rotational molding is a process generally used for producing hollowplastic products. By using additional post-molding operations, complexcomponents can be produced as effectively as other molding and extrusiontechniques. Rotational molding differs from other processing methods inthat the heating, melting, shaping, and cooling stages all occur afterthe polymer is placed in the mold, therefore no external pressure isapplied during forming. The rotational molding of polymers has beendescribed in Glenn Beall, “Rotational Molding: Design, Materials &Processing,” Hanser Gardner Publications, Cincinnati, Ohio (1998), whichis incorporated herein by reference in its entirety.

Blow molding can be used for making hollow plastics containers. Theprocess includes placing a softened polymer in the center of a mold,inflating the polymer against the mold walls with a blow pin, andsolidifying the product by cooling. There are three general types ofblow molding: extrusion blow molding, injection blow molding, andstretch blow molding. Injection blow molding can be used to processpolymers that cannot be extruded. Stretch blow molding can be used fordifficult to blow crystalline and crystallizable polymers such aspolypropylene. The blow molding of polymers has been described in NormanC. Lee, “Understanding Blow Molding,” Hanser Gardner Publications,Cincinnati, Ohio (2000), which is incorporated herein by reference inits entirety.

The following examples are presented to exemplify embodiments of theinvention. All numerical values are approximate. When numerical rangesare given, it should be understood that embodiments outside the statedranges may still fall within the scope of the invention. Specificdetails described in each example should not be construed as necessaryfeatures of the invention.

EXAMPLES

Testing Methods

In the examples that follow, the following analytical techniques areemployed:

GPC Method for Samples 1-4 and A-C

An automated liquid-handling robot equipped with a heated needle set to160° C. is used to add enough 1,2,4-trichlorobenzene stabilized with 300ppm Ionol to each dried polymer sample to give a final concentration of30 mg/mL. A small glass stir rod is placed into each tube and thesamples are heated to 160° C. for 2 hours on a heated, orbital-shakerrotating at 250 rpm. The concentrated polymer solution is then dilutedto 1 mg/ml using the automated liquid-handling robot and the heatedneedle set to 160° C.

A Symyx Rapid GPC system is used to determine the molecular weight datafor each sample. A Gilson 350 pump set at 2.0 ml/min flow rate is usedto pump helium-purged 1,2-dichlorobenzene stabilized with 300 ppm Ionolas the mobile phase through three Plgel 10 micrometer (μm) Mixed B 300mm×7.5 mm columns placed in series and heated to 160° C. A Polymer LabsELS 1000 Detector is used with the Evaporator set to 250° C., theNebulizer set to 165° C., and the nitrogen flow rate set to 1.8 SLM at apressure of 60-80 psi (400-600 kPa) N₂. The polymer samples are heatedto 160° C. and each sample injected into a 250 μl loop using theliquid-handling robot and a heated needle. Serial analysis of thepolymer samples using two switched loops and overlapping injections areused. The sample data is collected and analyzed using Symyx Epoch™software. Peaks are manually integrated and the molecular weightinformation reported uncorrected against a polystyrene standardcalibration curve.

Standard CRYSTAF Method

Branching distributions are determined by crystallization analysisfractionation (CRYSTAF) using a CRYSTAF 200 unit commercially availablefrom PolymerChar, Valencia, Spain. The samples are dissolved in 1,2,4trichlorobenzene at 160° C. (0.66 mg/mL) for 1 hr and stabilized at 95°C. for 45 minutes. The sampling temperatures range from 95 to 30° C. ata cooling rate of 0.2° C./min. An infrared detector is used to measurethe polymer solution concentrations. The cumulative solubleconcentration is measured as the polymer crystallizes while thetemperature is decreased. The analytical derivative of the cumulativeprofile reflects the short chain branching distribution of the polymer.

The CRYSTAF peak temperature and area are identified by the peakanalysis module included in the CRYSTAF Software (Version 2001.b,PolymerChar, Valencia, Spain). The CRYSTAF peak finding routineidentifies a peak temperature as a maximum in the dW/dT curve and thearea between the largest positive inflections on either side of theidentified peak in the derivative curve. To calculate the CRYSTAF curve,the preferred processing parameters are with a temperature limit of 70°C. and with smoothing parameters above the temperature limit of 0.1, andbelow the temperature limit of 0.3.

DSC Standard Method (Excluding Samples 14 and A-C)

Differential Scanning Calorimetry results are determined using a TAImodel Q1000 DSC equipped with an RCS cooling accessory and anautosampler. A nitrogen purge gas flow of 50 ml/min is used. The sampleis pressed into a thin film and melted in the press at about 175° C. andthen air-cooled to room temperature (25° C.). 3-10 mg of material isthen cut into a 6 mm diameter disk, accurately weighed, placed in alight aluminum pan (ca 50 mg), and then crimped shut. The thermalbehavior of the sample is investigated with the following temperatureprofile. The sample is rapidly heated to 180° C. and held isothermal for3 minutes in order to remove any previous thermal history. The sample isthen cooled to −40° C. at 10° C./min cooling rate and held at −40° C.for 3 minutes. The sample is then heated to 150° C. at 10° C./min.heating rate. The cooling and second heating curves are recorded.

The DSC melting peak is measured as the maximum in heat flow rate (W/g)with respect to the linear baseline drawn between −30° C. and end ofmelting. The heat of fusion is measured as the area under the meltingcurve between −30° C. and the end of melting using a linear baseline.

GPC Method (Excluding Samples 14 and A-C)

The gel permeation chromatographic system consists of either a PolymerLaboratories Model PL-210 or a Polymer Laboratories Model PL-220instrument. The column and carousel compartments are operated at 140° C.Three Polymer Laboratories 10-micron Mixed-B columns are used. Thesolvent is 1,2,4 trichlorobenzene. The samples are prepared at aconcentration of 0.1 grams of polymer in 50 milliliters of solventcontaining 200 ppm of butylated hydroxytoluene (BHT). Samples areprepared by agitating lightly for 2 hours at 160° C. The injectionvolume used is 100 microliters and the flow rate is 1.0 ml/minute.

Calibration of the GPC column set is performed with 21 narrow molecularweight distribution polystyrene standards with molecular weights rangingfrom 580 to 8,400,000, arranged in 6 “cocktail” mixtures with at least adecade of separation between individual molecular weights. The standardsare purchased from Polymer Laboratories (Shropshire, UK). Thepolystyrene standards are prepared at 0.025 grams in 50 milliliters ofsolvent for molecular weights equal to or greater than 1,000,000, and0.05 grams in 50 milliliters of solvent for molecular weights less than1,000,000. The polystyrene standards are dissolved at 80° C. with gentleagitation for 30 minutes. The narrow standards mixtures are run firstand in order of decreasing highest molecular weight component tominimize degradation. The polystyrene standard peak molecular weightsare converted to polyethylene molecular weights using the followingequation (as described in Williams and Ward, J. Polym. Sci., Polym.Let., 6, 621 (1968)): M_(polyethylene)=0.431 (M_(polystyrene)).

Polyethylene equivalent molecular weight calculations are performedusing Viscotek TriSEC software Version 3.0.

Compression Set

Compression set is measured according to ASTM D 395. The sample isprepared by stacking 25.4 mm diameter round discs of 3.2 mm, 2.0 mm, and0.25 mm thickness until a total thickness of 12.7 mm is reached. Thediscs are cut from 12.7 cm×12.7 cm compression molded plaques moldedwith a hot press under the following conditions: zero pressure for 3 minat 190° C., followed by 86 MPa for 2 min at 190° C., followed by coolinginside the press with cold running water at 86 MPa.

Density

Samples for density measurement are prepared according to ASTM D 1928.Measurements are made within one hour of sample pressing using ASTMD792, Method B.

Flexural/Secant Modulus/Storage Modulus

Samples are compression molded using ASTM D 1928. Flexural and 2 percentsecant moduli are measured according to ASTM D-790. Storage modulus ismeasured according to ASTM D 5026-01 or equivalent technique.

Optical Properties

Films of 0.4 mm thickness are compression molded using a hot press(Carver Model #40954PR1001R). The pellets are placed betweenpolytetrafluoroethylene sheets, heated at 190° C. at 55 psi (380 kPa)for 3 min, followed by 1.3 MPa for 3 min, and then 2.6 MPa for 3 min.The film is then cooled in the press with running cold water at 1.3 MPafor 1 min. The compression molded films are used for opticalmeasurements, tensile behavior, recovery, and stress relaxation.

Clarity is measured using BYK Gardner Haze-gard as specified in ASTM D1746.

45° gloss is measured using BYK Gardner Glossmeter Microgloss 45° asspecified in ASTM D-2457

Internal haze is measured using BYK Gardner Haze-gard based on ASTM D1003 Procedure A. Mineral oil is applied to the film surface to removesurface scratches.

Mechanical Properties—Tensile, Hysteresis, and Tear

Stress-strain behavior in uniaxial tension is measured using ASTM D 1708microtensile specimens. Samples are stretched with an Instron at 500%min⁻¹ at 21° C. Tensile strength and elongation at break are reportedfrom an average of 5 specimens.

100% and 300% Hysteresis is determined from cyclic loading to 100% and300% strains using ASTM D 1708 microtensile specimens with an Instron™instrument. The sample is loaded and unloaded at 267% min⁻¹ for 3 cyclesat 21° C. Cyclic experiments at 300% and 80° C. are conducted using anenvironmental chamber. In the 80° C. experiment, the sample is allowedto equilibrate for 45 minutes at the test temperature before testing. Inthe 21° C., 300% strain cyclic experiment, the retractive stress at 150%strain from the first unloading cycle is recorded. Percent recovery forall experiments are calculated from the first unloading cycle using thestrain at which the load returned to the base line. The percent recoveryis defined as:${\%\quad{Recovery}} = {\frac{ɛ_{f} - ɛ_{s}}{ɛ_{f}} \times 100}$

where ε_(f) is the strain taken for cyclic loading and ε_(s) is thestrain where the load returns to the baseline during the 1^(st)unloading cycle.

Stress relaxation is measured at 50 percent strain and 37° C. for 12hours using an Instron™ instrument equipped with an environmentalchamber. The gauge geometry was 76 mm×25 mm×0.4 mm. After equilibratingat 37° C. for 45 min in the environmental chamber, the sample wasstretched to 50% strain at 333% min⁻¹. Stress was recorded as a functionof time for 12 hours. The percent stress relaxation after 12 hours wascalculated using the formula:${\%{\quad\quad}{Stress}{\quad\quad}{Relaxation}} = {\frac{L_{0} - L_{12}}{L_{0}} \times 100}$where L₀ is the load at 50% strain at 0 time and L₁₂ is the load at 50percent strain after 12 hours.

Tensile notched tear experiments are carried out on samples having adensity of 0.88 g/cc or less using an Instron™ instrument. The geometryconsists of a gauge section of 76 mm×13 mm×0.4 mm with a 2 mm notch cutinto the sample at half the specimen length. The sample is stretched at508 mm min⁻¹ at 21° C. until it breaks. The tear energy is calculated asthe area under the stress-elongation curve up to strain at maximum load.An average of at least 3 specimens are reported.

TMA

Thermal Mechanical Analysis (Penetration Temperature) is conducted on 30mm diameter×3.3 mm thick, compression molded discs, formed at 180° C.and 10 MPa molding pressure for 5 minutes and then air quenched. Theinstrument used is a TMA 7, brand available from Perkin-Elmer. In thetest, a probe with 1.5 mm radius tip (P/N N519-0416) is applied to thesurface of the sample disc with 1N force. The temperature is raised at5° C./min from 25° C. The probe penetration distance is measured as afunction of temperature. The experiment ends when the probe haspenetrated 1 mm into the sample.

DMA

Dynamic Mechanical Analysis (DMA) is measured on compression moldeddisks formed in a hot press at 180° C. at 10 MPa pressure for 5 minutesand then water cooled in the press at 90° C./min. Testing is conductedusing an ARES controlled strain rheometer (TA instruments) equipped withdual cantilever fixtures for torsion testing.

A 1.5 mm plaque is pressed and cut in a bar of dimensions 32×12 mm. Thesample is clamped at both ends between fixtures separated by 10 mm (gripseparation ΔL) and subjected to successive temperature steps from −100°C. to 200° C. (5° C. per step). At each temperature the torsion modulusG′ is measured at an angular frequency of 10 rad/s, the strain amplitudebeing maintained between 0.1 percent and 4 percent to ensure that thetorque is sufficient and that the measurement remains in the linearregime.

An initial static force of 10 g is maintained (auto-tension mode) toprevent slack in the sample when thermal expansion occurs. As aconsequence, the grip separation ΔL increases with the temperature,particularly above the melting or softening point of the polymer sample.The test stops at the maximum temperature or when the gap between thefixtures reaches 65 mm.

Melt Index

Melt index, or 12, is measured in accordance with ASTM D 1238, Condition190° C./2.16 kg. Melt index, or I₁₀ is also measured in accordance withASTM D 1238, Condition 190° C./10 kg.

ATREF

Analytical temperature rising elution fractionation (ATREF) analysis isconducted according to the method described in U.S. Pat. No. 4,798,081and Wilde, L.; Ryle, T. R.; Knobeloch, D. C.; Peat, I. R.; Determinationof Branching Distributions in Polyethylene and Ethylene Copolymers, J.Polym. Sci., 20, 441-455 (1982), which are incorporated by referenceherein in their entirety. The composition to be analyzed is dissolved intrichlorobenzene and allowed to crystallize in a column containing aninert support (stainless steel shot) by slowly reducing the temperatureto 20° C. at a cooling rate of 0.1° C./min. The column is equipped withan infrared detector. An ATREF chromatogram curve is then generated byeluting the crystallized polymer sample from the column by slowlyincreasing the temperature of the eluting solvent (trichlorobenzene)from 20 to 120° C. at a rate of 1.5° C./min.

¹³C NMR Analysis

The samples are prepared by adding approximately 3 g of a 50/50 mixtureof tetrachloroethane-d²/orthodichlorobenzene to 0.4 g sample in a 10 mmNMR tube. The samples are dissolved and homogenized by heating the tubeand its contents to 150° C. The data are collected using a JEOL Eclipse™400 MHz spectrometer or a Varian Unity Plus™ 400 MHz spectrometer,corresponding to a ¹³C resonance frequency of 100.5 MHz. The data areacquired using 4000 transients per data file with a 6 second pulserepetition delay. To achieve minimum signal-to-noise for quantitativeanalysis, multiple data files are added together. The spectral width is25,000 Hz with a minimum file size of 32 K data points. The samples areanalyzed at 130° C. in a 10 mm broad band probe. The comonomerincorporation is determined using Randall's triad method (Randall, J.C.; JMS-Rev. Macromol. Chem. Phys., C29, 201-317 (1989), which isincorporated by reference herein in its entirety.

Polymer Fractionation by TREF

Large-scale TREF fractionation is carried by dissolving 15-20 g ofpolymer in 2 liters of 1,2,4-trichlorobenzene (TCB)by stirring for 4hours at 160° C. The polymer solution is forced by 15 psig (100 kPa)nitrogen onto a 3 inch by 4 foot (7.6 cm×12 cm) steel column packed witha 60:40 (v:v) mix of 30-40 mesh (600-425 μm) spherical, technicalquality glass beads (available from Potters Industries, HC 30 Box 20,Brownwood, Tex., 76801) and stainless steel, 0.028″ (0.7 mm) diametercut wire shot (available from Pellets, Inc. 63 Industrial Drive, NorthTonawanda, N.Y., 14120). The column is immersed in a thermallycontrolled oil jacket, set initially to 160° C. The column is firstcooled ballistically to 125° C., then slow cooled to 20° C. at 0.04° C.per minute and held for one hour. Fresh TCB is introduced at about 65ml/min while the temperature is increased at 0.167° C. per minute.

Approximately 2000 ml portions of eluant from the preparative TREFcolumn are collected in a 16 station, heated fraction collector. Thepolymer is concentrated in each fraction using a rotary evaporator untilabout 50 to 100 ml of the polymer solution remains. The concentratedsolutions are allowed to stand overnight before adding excess methanol,filtering, and rinsing (approx. 300-500 ml of methanol including thefinal rinse). The filtration step is performed on a 3 position vacuumassisted filtering station using 5.0 μm polytetrafluoroethylene coatedfilter paper (available from Osmonics Inc., Cat# Z50WP04750). Thefiltrated fractions are dried overnight in a vacuum oven at 60° C. andweighed on an analytical balance before further testing.

Melt Strength

Melt Strength (MS) is measured by using a capillary rheometer fittedwith a 2.1 mm diameter, 20:1 die with an entrance angle of approximately45 degrees. After equilibrating the samples at 190° C. for 10 minutes,the piston is run at a speed of 1 inch/minute (2.54 cm/minute). Thestandard test temperature is 190° C. The sample is drawn uniaxially to aset of accelerating nips located 100 mm below the die with anacceleration of 2.4 mm/sec². The required tensile force is recorded as afunction of the take-up speed of the nip rolls. The maximum tensileforce attained during the test is defined as the melt strength. In thecase of polymer melt exhibiting draw resonance, the tensile force beforethe onset of draw resonance was taken as melt strength. The meltstrength is recorded in centiNewtons (“cN”).

Catalysts

The term “overnight”, if used, refers to a time of approximately 16-18hours, the term “room temperature”, refers to a temperature of 20-25°C., and the term “mixed alkanes” refers to a commercially obtainedmixture of C₆₋₉ aliphatic hydrocarbons available under the tradedesignation Isopar E®, from ExxonMobil Chemical Company. In the eventthe name of a compound herein does not conform to the structuralrepresentation thereof, the structural representation shall control. Thesynthesis of all metal complexes and the preparation of all screeningexperiments were carried out in a dry nitrogen atmosphere using dry boxtechniques. All solvents used were HPLC grade and were dried beforetheir use.

MMAO refers to modified methylalumoxane, a triisobutylaluminum modifiedmethylalumoxane available commercially from Akzo-Noble Corporation. Thepreparation of catalyst (B1) is conducted as follows.

a. Preparation of(1-methylethyl)(2-hydroxy-3,5-di(t-butyl)phenyl)methylimine

3,5-Di-t-butylsalicylaldehyde (3.00 g) is added to 10 mL ofisopropylamine. The solution rapidly turns bright yellow. After stirringat ambient temperature for 3 hours, volatiles are removed under vacuumto yield a bright yellow, crystalline solid (97 percent yield).

b) Preparation of1,2-bis-(3,5-di-t-butylphenylene)(1-(N-(1-methylethyl)immino)methyl)(2-oxoyl)zirconiumdibenzyl

A solution of (1-methylethyl)(2-hydroxy-3,5-di(t-butyl)phenyl)imine (605mg, 2.2 mmol) in 5 mL toluene is slowly added to a solution ofZr(CH₂Ph)₄ (500 mg, 1.1 mmol) in 50 mL toluene. The resulting darkyellow solution is stirred for 30 min. Solvent is removed under reducedpressure to yield the desired product as a reddish-brown solid. Thepreparation of catalyst (B2) is conducted as follows.

a. Preparation of(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)imine

2-Methylcyclohexylamine (8.44 mL, 64.0 mmol) is dissolved in methanol(90 mL), and di-t-butylsalicaldehyde (10.00 g, 42.67 mmol) is added. Thereaction mixture is stirred for three hours and then cooled to −25° C.for 12 hrs. The resulting yellow solid precipitate is collected byfiltration and washed with cold methanol (2×15 mL), and then dried underreduced pressure. The yield is 11.17 g of a yellow solid. ¹H NMR isconsistent with the desired product as a mixture of isomers.

b) Preparation ofbis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino)zirconiumdibenzyl

A solution of(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)imine (7.63g, 23.2 mmol) in 200 mL toluene is slowly added to a solution ofZr(CH₂Ph)₄ (5.28 g, 11.6 mmol) in 600 mL toluene. The resulting darkyellow solution is stirred for 1 hour at 25° C. The solution is dilutedfurther with 680 mL toluene to give a solution having a concentration of0.00783 M.

Cocatalyst 1 A mixture of methyldi(C₁₄₋₁₈ alkyl)ammonium salts oftetrakis(pentafluorophenyl)borate (here-in-after armeenium borate),prepared by reaction of a long chain trialkylamine (Armeen™ M2HT,available from Akzo-Nobel, Inc.), HCl and Li[B(C₆F₅)₄], substantially asdisclosed in U.S. Pat. No. 5,919,9883, Ex. 2.

Cocatalyst 2 Mixed C₁₄₋₁₈ alkyldimethylammonium salt ofbis(tris(pentafluorophenyl)-alumane)-2-undecylimidazolide, preparedaccording to U.S. Pat. NO. 6,395,671, Ex. 16.

Shuttling Agents The shuttling agents employed include diethylzinc (DEZ,SA1), di(i-butyl)zinc (SA2), di(n-hexyl)zinc (SA3), triethylaluminum(TEA, SA4), trioctylaluminum (SA5), triethylgallium (SA6),i-butylaluminum bis(dimethyl(t-butyl)siloxane) (SA7), i-butylaluminumbis(di(trimethylsilyl)amide) (SA8), n-octylaluminumdi(pyridine-2-methoxide) (SA9), bis(n-octadecyl)i-butylaluminum (SA10),i-butylaluminum bis(di(n-pentyl)amide) (SA11), n-octylaluminumbis(2,6-di-t-butylphenoxide) (SA12), n-octylaluminumdi(ethyl(1-naphthyl)amide) (SA13), ethylaluminumbis(t-butyldimethylsiloxide) (SA14), ethylaluminumdi(bis(trimethylsilyl)amide) (SA15), ethylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide) (SA16), n-octylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide) (SA 17), n-octylaluminumbis(dimethyl(t-butyl)siloxide (SA18), ethylzinc (2,6-diphenylphenoxide)(SA19), and ethylzinc (t-butoxide) (SA20).

Examples 1-4, Comparative Examples A*-C*

General High Throughput Parallel Polymerization Conditions

Polymerizations are conducted using a high throughput, parallelpolymerization reactor (PPR) available from Symyx technologies, Inc. andoperated substantially according to U.S. Pat. Nos. 6,248,540, 6,030,917,6,362,309, 6,306,658, and 6,316,663. Ethylene copolymerizations areconducted at 130° C. and 200 psi (1.4 MPa) with ethylene on demand using1.2 equivalents of cocatalyst 1 based on total catalyst used (1.1equivalents when MMAO is present). A series of polymerizations areconducted in a parallel pressure reactor (PPR) contained of 48individual reactor cells in a 6×8 array that are fitted with apre-weighed glass tube. The working volume in each reactor cell is 6000μL. Each cell is temperature and pressure controlled with stirringprovided by individual stirring paddles. The monomer gas and quench gasare plumbed directly into the PPR unit and controlled by automaticvalves. Liquid reagents are robotically added to each reactor cell bysyringes and the reservoir solvent is mixed alkanes. The order ofaddition is mixed alkanes solvent (4 ml), ethylene, 1-octene comonomer(1 ml), cocatalyst 1 or cocatalyst 1/MMAO mixture, shuttling agent, andcatalyst or catalyst mixture. When a mixture of cocatalyst 1 and MMAO ora mixture of two catalysts is used, the reagents are premixed in a smallvial immediately prior to addition to the reactor. When a reagent isomitted in an experiment, the above order of addition is otherwisemaintained. Polymerizations are conducted for approximately 1-2 minutes,until predetermined ethylene consumptions are reached. After quenchingwith CO, the reactors are cooled and the glass tubes are unloaded. Thetubes are transferred to a centrifuge/vacuum drying unit, and dried for12 hours at 60° C. The tubes containing dried polymer are weighed andthe difference between this weight and the tare weight gives the netyield of polymer. Results are contained in Table 1. In Table 1 andelsewhere in the application, comparative compounds are indicated by anasterisk (*).

Examples 1-4 demonstrate the synthesis of linear block copolymers by thepresent invention as evidenced by the formation of a very narrow MWD,essentially monomodal copolymer when DEZ is present and a bimodal, broadmolecular weight distribution product (a mixture of separately producedpolymers) in the absence of DEZ. Due to the fact that Catalyst (A1) isknown to incorporate more octene than Catalyst (B1), the differentblocks or segments of the resulting copolymers of the invention aredistinguishable based on branching or density. TABLE 1 Cat. (A1) Cat(B1) Cocat MMAO shuttling Ex. (μmol) (μmol) (μmol) (μmol) agent (μmol)Yield (g) Mn Mw/Mn hexyls¹ A* 0.06 — 0.066 0.3 — 0.1363 300502 3.32 — B*— 0.1 0.110 0.5 — 0.1581 36957 1.22 2.5 C* 0.06 0.1 0.176 0.8 — 0.203845526 5.30² 5.5 1 0.06 0.1 0.192 — DEZ (8.0) 0.1974 28715 1.19 4.8 20.06 0.1 0.192 — DEZ (80.0) 0.1468 2161 1.12 14.4 3 0.06 0.1 0.192 — TEA(8.0) 0.208 22675 1.71 4.6 4 0.06 0.1 0.192 — TEA (80.0) 0.1879 33381.54 9.4¹C₆ or higher chain content per 1000 carbons²Bimodal molecular weight distribution

It may be seen the polymers produced according to the invention have arelatively narrow polydispersity (Mw/Mn) and larger block-copolymercontent (trimer, tetramer, or larger) than polymers prepared in theabsence of the shuttling agent.

Further characterizing data for the polymers of Table 1 are determinedby reference to the figures. More specifically DSC and ATREF resultsshow the following:

The DSC curve for the polymer of example 1 shows a 115.7° C. meltingpoint (Tm) with a heat of fusion of 158.1 J/g. The corresponding CRYSTAFcurve shows the tallest peak at 34.5° C. with a peak area of 52.9percent. The difference between the DSC Tm and the Tcrystaf is 81.2° C.

The DSC curve for the polymer of example 2 shows a peak with a 109.7° C.melting point (Tm) with a heat of fusion of 214.0 J/g. The correspondingCRYSTAF curve shows the tallest peak at 46.2° C. with a peak area of57.0 percent. The difference between the DSC Tm and the Tcrystaf is63.5° C.

The DSC curve for the polymer of example 3 shows a peak with a 120.7° C.melting point (Tm) with a heat of fusion of 160.1 J/g. The correspondingCRYSTAF curve shows the tallest peak at 66.1° C. with a peak area of71.8 percent. The difference between the DSC Tm and the Tcrystaf is54.6° C.

The DSC curve for the polymer of example 4 shows a peak with a 104.5° C.melting point (Tm) with a heat of fusion of 170.7 J/g. The correspondingCRYSTAF curve shows the tallest peak at 30° C. with a peak area of 18.2percent. The difference between the DSC Tm and the Tcrystaf is 74.5° C.

The DSC curve for Comparative Example A* shows a 90.0° C. melting point(Tm) with a heat of fusion of 86.7 J/g. The corresponding CRYSTAF curveshows the tallest peak at 48.5° C. with a peak area of 29.4 percent.Both of these values are consistent with a resin that is low in density.The difference between the DSC Tm and the Tcrystaf is 41.8° C.

The DSC curve for Comparative Example B* shows a 129.8° C. melting point(Tm) with a heat of fusion of 237.0 J/g. The corresponding CRYSTAF curveshows the tallest peak at 82.4° C. with a peak area of 83.7 percent.Both of these values are consistent with a resin that is high indensity. The difference between the DSC Tm and the Tcrystaf is 47.4° C.

The DSC curve for Comparative Example C* shows a 125.3° C. melting point(Tm) with a heat of fusion of 143.0 J/g. The corresponding CRYSTAF curveshows the tallest peak at 81.8° C. with a peak area of 34.7 percent aswell as a lower crystalline peak at 52.4° C. The separation between thetwo peaks is consistent with the presence of a high crystalline and alow crystalline polymer. The difference between the DSC Tm and theTcrystaf is 43.5° C.

Examples 5-19, Comparative Examples D*-F* Continuous SolutionPolymerization, Catalyst A1/B2 +DEZ

Continuous solution polymerizations are carried out in a computercontrolled autoclave reactor equipped with an internal stirrer. Purifiedmixed alkanes solvent (Isopar™ E available from ExxonMobil ChemicalCompany), ethylene at 2.70 lbs/hour (1.22 kg/hour), 1-octene, andhydrogen (where used) are supplied to a 3.8 L reactor equipped with ajacket for temperature control and an internal thermocouple. The solventfeed to the reactor is measured by a mass-flow controller. A variablespeed diaphragm pump controls the solvent flow rate and pressure to thereactor. At the discharge of the pump, a side stream is taken to provideflush flows for the catalyst and cocatalyst I injection lines and thereactor agitator. These flows are measured by Micro-Motion mass flowmeters and controlled by control valves or by the manual adjustment ofneedle valves. The remaining solvent is combined with 1-octene,ethylene, and hydrogen (where used) and fed to the reactor. A mass flowcontroller is used to deliver hydrogen to the reactor as needed. Thetemperature of the solvent/monomer solution is controlled by use of aheat exchanger before entering the reactor. This stream enters thebottom of the reactor. The catalyst component solutions are meteredusing pumps and mass flow meters and are combined with the catalystflush solvent and introduced into the bottom of the reactor. The reactoris run liquid-full at 500 psig (3.45 MPa) with vigorous stirring.Product is removed through exit lines at the top of the reactor. Allexit lines from the reactor are steam traced and insulated.Polymerization is stopped by the addition of a small amount of waterinto the exit line along with any stabilizers or other additives andpassing the mixture through a static mixer. The product stream is thenheated by passing through a heat exchanger before devolatilization. Thepolymer product is recovered by extrusion using a devolatilizingextruder and water cooled pelletizer. Process details and results arecontained in Table 2. Selected polymer properties are provided in Table3. TABLE 2 Process details for preparation of exemplary polymers Cat CatA1 Cat B2 DEZ Cocat Cocat Poly C₈H₁₆ Solv. H₂ T A1² Flow B2³ Flow DEZFlow Conc. Flow [C₂H₄]/ Rate⁵ Ex. kg/hr kg/hr sccm¹ ° C. ppm kg/hr ppmkg/hr Conc % kg/hr ppm kg/hr [DEZ]⁴ kg/hr Conv %⁶ Solids % Eff.⁷ D* 1.6312.7 29.90 120 142.2  0.14 — — 0.19 0.32  820 0.17 536 1.81 88.8 11.295.2 E* ″  9.5 5.00 ″ — — 109 0.10 0.19 ″ 1743 0.40 485 1.47 89.9 11.3126.8 F* ″ 11.3 251.6 ″ 71.7 0.06 30.8 0.06 — — ″ 0.11 — 1.55 88.5 10.3257.7  5 ″ ″ — ″ ″ 0.14 30.8 0.13 0.17 0.43 ″ 0.26 419 1.64 89.6 11.1118.3  6 ″ ″ 4.92 ″ ″ 0.10 30.4 0.08 0.17 0.32 ″ 0.18 570 1.65 89.3 11.1172.7  7 ″ ″ 21.70 ″ ″ 0.07 30.8 0.06 0.17 0.25 ″ 0.13 718 1.60 89.210.6 244.1  8 ″ ″ 36.90 ″ ″ 0.06 ″ ″ ″ 0.10 ″ 0.12 1778  1.62 90.0 10.8261.1  9 ″ ″ 78.43 ″ ″ ″ ″ ″ ″ 0.04 ″ ″ 4596  1.63 90.2 10.8 267.9 10 ″″ 0.00 123 71.1 0.12 30.3 0.14 0.34 0.19 1743 0.08 415 1.67 90.31 11.1131.1 11 ″ ″ ″ 120 71.1 0.16 ″ 0.17 0.80 0.15 1743 0.10 249 1.68 89.5611.1 100.6 12 ″ ″ ″ 121 71.1 0.15 ″ 0.07 ″ 0.09 1743 0.07 396 1.70 90.0211.3 137.0 13 ″ ″ ″ 122 71.1 0.12 ″ 0.06 ″ 0.05 1743 0.05 653 1.69 89.6411.2 161.9 14 ″ ″ ″ 120 71.1 0.05 ″ 0.29 ″ 0.10 1743 0.10 395 1.41 89.429.3 114.1 15 2.45 ″ ″ ″ 71.1 0.14 ″ 0.17 ″ 0.14 1743 0.09 282 1.80 89.3311.3 121.3 16 ″ ″ ″ 122 71.1 0.10 ″ 0.13 ″ 0.07 1743 0.07 485 1.78 90.1111.2 159.7 17 ″ ″ ″ 121 71.1 0.10 ″ 0.14 ″ 0.08 1743 ″ 506 1.75 89.0811.0 155.6 18 0.69 ″ ″ 121 71.1 ″ ″ 0.22 ″ 0.11 1743 0.10 331 1.25 89.938.8 90.2 19 0.32 ″ ″ 122 71.1 0.06 ″ ″ ″ 0.09 1743 0.08 367 1.16 90.748.4 106.0*Comparative, not an example of the invention¹standard cm³/min²[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl³bis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino)zirconium dibenzyl⁴molar ratio in reactor⁵polymer production rate⁶percent ethylene conversion in reactor⁷efficiency, kg polymer/g M where g M = g Hf + g Zr

TABLE 3 Properties of exemplary polymers Heat of Tm- CRYSTAF Density MwMn Fusion T_(m) T_(c) T_(CRYSTAF) T_(CRYSTAF) Peak Area Ex. (g/cm³) I₂I₁₀ I₁₀/I₂ (g/mol) (g/mol) Mw/Mn (J/g) (° C.) (° C.) (° C.) (° C.)(percent) D* 0.8627 1.5 10.0 6.5 110,000 55,800 2.0 32 37 45 30 7 99 E*0.9378 7.0 39.0 5.6 65,000 33,300 2.0 183 124 113 79 45 95 F* 0.8895 0.912.5 13.4 137,300 9,980 13.8 90 125 111 78 47 20  5 0.8786 1.5 9.8 6.7104,600 53,200 2.0 55 120 101 48 72 60  6 0.8785 1.1 7.5 6.5 10960053300 2.1 55 115 94 44 71 63  7 0.8825 1.0 7.2 7.1 118,500 53,100 2.2 69121 103 49 72 29  8 0.8828 0.9 6.8 7.7 129,000 40,100 3.2 68 124 106 8043 13  9 0.8836 1.1 9.7 9.1 129600 28700 4.5 74 125 109 81 44 16 100.8784 1.2 7.5 6.5 113,100 58,200 1.9 54 116 92 41 75 52 11 0.8818 9.159.2 6.5 66,200 36,500 1.8 63 114 93 40 74 25 12 0.8700 2.1 13.2 6.4101,500 55,100 1.8 40 113 80 30 83 91 13 0.8718 0.7 4.4 6.5 132,10063,600 2.1 42 114 80 30 81 8 14 0.9116 2.6 15.6 6.0 81,900 43,600 1.9123 121 106 73 48 92 15 0.8719 6.0 41.6 6.9 79,900 40,100 2.0 33 114 9132 82 10 16 0.8758 0.5 3.4 7.1 148,500 74,900 2.0 43 117 96 48 69 65 170.8757 1.7 11.3 6.8 107,500 54,000 2.0 43 116 96 43 73 57 18 0.9192 4.124.9 6.1 72,000 37,900 1.9 136 120 106 70 50 94 19 0.9344 3.4 20.3 6.076,800 39,400 1.9 169 125 112 80 45 88

The resulting polymers are tested by DSC and ATREF as with previousexamples. Results are as follows:

The DSC curve for the polymer of example 5 shows a peak with a 119.6° C.melting point (Tm) with a heat of fusion of 60.0 J/g. The correspondingCRYSTAF curve shows the tallest peak at 47.6° C. with a peak area of59.5 percent. The delta between the DSC Tm and the Tcrystaf is 72.0° C.

The DSC curve for the polymer of example 6 shows a peak with a 115.2° C.melting point (Tm) with a heat of fusion of 60.4 J/g. The correspondingCRYSTAF curve shows the tallest peak at 44.2° C. with a peak area of62.7 percent. The delta between the DSC Tm and the Tcrystaf is 71.0° C.

The DSC curve for the polymer of example 7 shows a peak with a 121.3° C.melting point with a heat of fusion of 69.1 J/g. The correspondingCRYSTAF curve shows the tallest peak at 49.2° C. with a peak area of29.4 percent. The delta between the DSC Tm and the Tcrystaf is 72.1° C.

The DSC curve for the polymer of example 8 shows a peak with a 123.5° C.melting point (Tm) with a heat of fusion of 67.9 J/g. The correspondingCRYSTAF curve shows the tallest peak at 80. 1° C. with a peak area of12.7 percent. The delta between the DSC Tm and the Tcrystaf is 43.4° C.

The DSC curve for the polymer of example 9 shows a peak with a 124.6° C.melting point (Tm) with a heat of fusion of 73.5 J/g. The correspondingCRYSTAF curve shows the tallest peak at 80.8° C. with a peak area of16.0 percent. The delta between the DSC Tm and the Tcrystaf is 43.8° C.

The DSC curve for the polymer of example 10 shows a peak with a 115.6°C. melting point (Tm) with a heat of fusion of 60.7 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 40.9° C. with apeak area of 52.4 percent. The delta between the DSC Tm and the Tcrystafis 74.7° C.

The DSC curve for the polymer of example 11 shows a peak with a 113.6°C. melting point (Tm) with a heat of fusion of 70.4 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 39.6° C. with apeak area of 25.2 percent. The delta between the DSC Tm and the Tcrystafis 74.1° C.

The DSC curve for the polymer of example 12 shows a peak with a 113.2°C. melting point (Tm) with a heat of fusion of 48.9 J/g. Thecorresponding CRYSTAF curve shows no peak equal to or above 30° C.(Tcrystaf for purposes of further calculation is therefore set at 30°C.). The delta between the DSC Tm and the Tcrystaf is 83.2° C.

The DSC curve for the polymer of example 13 shows a peak with a 114.4°C. melting point (Tm) with a heat of fusion of 49.4 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 33.8° C. with apeak area of 7.7 percent. The delta between the DSC Tm and the Tcrystafis 84.4° C.

The DSC for the polymer of example 14 shows a peak with a 120.8° C.melting point (Tm) with a heat of fusion of 127.9 J/g. The correspondingCRYSTAF curve shows the tallest peak at 72.9° C. with a peak area of92.2 percent. The delta between the DSC Tm and the Tcrystaf is 47.9° C.

The DSC curve for the polymer of example 15 shows a peak with a 114.3°C. melting point (Tm) with a heat of fusion of 36.2 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 32.3° C. with apeak area of 9.8 percent. The delta between the DSC Tm and the Tcrystafis 82.0° C.

The DSC curve for the polymer of example 16 shows a peak with a 116.6°C. melting point (Tm) with a heat of fusion of 44.9 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 48.0° C. with apeak area of 65.0 percent. The delta between the DSC Tm and the Tcrystafis 68.6° C.

The DSC curve for the polymer of example 17 shows a peak with a 116.0°C. melting point (Tm) with a heat of fusion of 47.0 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 43.1° C. with apeak area of 56.8 percent. The delta between the DSC Tm and the Tcrystafis 72.9° C.

The DSC curve for the polymer of example 18 shows a peak with a 120.5°C. melting point (Tm) with a heat of fusion of 141.8 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 70.0° C. with apeak area of 94.0 percent. The delta between the DSC Tm and the Tcrystafis 50.5° C.

The DSC curve for the polymer of example 19 shows a peak with a 124.8°C. melting point (Tm) with a heat of fusion of 174.8 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 79.9° C. with apeak area of 87.9 percent. The delta between the DSC Tm and the Tcrystafis 45.0° C.

The DSC curve for the polymer of Comparative Example D* shows a peakwith a 37.3° C. melting point (Tm) with a heat of fusion of 31.6 J/g.The corresponding CRYSTAF curve shows no peak equal to and above 30° C.Both of these values are consistent with a resin that is low in density.The delta between the DSC Tm and the Tcrystaf is 7.3° C.

The DSC curve for the polymer of Comparative Example E* shows a peakwith a 124.0° C. melting point (Tm) with a heat of fusion of 179.3 J/g.The corresponding CRYSTAF curve shows the tallest peak at 79.3° C. witha peak area of 94.6 percent. Both of these values are consistent with aresin that is high in density. The delta between the DSC Tm and theTcrystaf is 44.6° C.

The DSC curve for the polymer of Comparative Example F* shows a peakwith a 124.8° C. melting point (Tm) with a heat of fusion of 90.4 J/g.The corresponding CRYSTAF curve shows the tallest peak at 77.6° C. witha peak area of 19.5 percent. The separation between the two peaks isconsistent with the presence of both a high crystalline and a lowcrystalline polymer. The delta between the DSC Tm and the Tcrystaf is47.2° C.

Physical Property Testing

Polymer samples are evaluated for physical properties such as hightemperature resistance properties, as evidenced by TMA temperaturetesting, pellet blocking strength, high temperature recovery, hightemperature compression set and storage modulus ratio, G′(25°C.)/G′(100° C.). Several commercially available polymers are included inthe tests: Comparative Example G* is a substantially linearethylene/l-octene copolymer (AFFINITY®, available from The Dow ChemicalCompany), Comparative Example H* is an elastomeric, substantially linearethylene/1-octene copolymer (AFFINITY® EG8 100, available from The DowChemical Company), Comparative Example I* is a substantially linearethylene/1-octene copolymer (AFFINITY®PL1840, available from The DowChemical Company), Comparative Example J* is a hydrogenatedstyrene/butadiene/styrene triblock copolymer (KRATON™ G 1652, availablefrom KRATON Polymers), Comparative Example K* is a thermoplasticvulcanizate (TPV, a polyolefin blend containing dispersed therein acrosslinked elastomer). Results are presented in Table 4. TABLE 4 HighTemperature Mechanical Properties 300% Pellet Strain TMA-1 mm BlockingRecovery Compression penetration Strength G′(25° C.)/ (80° C.) Set (70°C.) Ex. (° C.) lb/ft² (kPa) G′(100° C.) (percent) (percent) D* 51 — 9Failed — E* 130 — 18 — — F* 70 141 (6.8) 9 Failed 100   5 104  0 (0) 681 49  6 110 — 5 — 52  7 113 — 4 84 43  8 111 — 4 Failed 41  9 97 — 4 —66 10 108 — 5 81 55 11 100 — 8 — 68 12 88 — 8 — 79 13 95 — 6 84 71 14125 — 7 — — 15 96 — 5 — 58 16 113 — 4 — 42 17 108  0 (0) 4 82 47 18 125— 10 — — 19 133 — 9 — — G* 75 463 (22.2) 89 Failed 100  H* 70 213 (10.2)29 Failed 100  I* 111 — 11 — — J* 107 — 5 Failed 100  K* 152 — 3 — 40

In Table 4, Comparative Example F* (which is a physical blend of the twopolymers resulting from simultaneous polymerizations using catalyst A1and B1) has a 1 mm penetration temperature of about 70° C., whileExamples 5-9 have a 1 mm penetration temperature of 100° C. or greater.Further, examples 10-19 all have a 1 mm penetration temperature ofgreater than 85° C., with most having 1 mm TMA temperature of greaterthan 90° C. or even greater than 100° C. This shows that the novelpolymers have better dimensional stability at higher temperaturescompared to a physical blend. Comparative Example J* (a commercial SEBS)has a good 1 mm TMA temperature of about 107° C., but it has very poor(high temperature 70° C.) compression set of about 100 percent and italso failed to recover (sample broke) during a high temperature (80° C.)300 percent strain recovery. Thus the exemplified polymers have a uniquecombination of properties unavailable even in some commerciallyavailable, high performance thermoplastic elastomers.

Similarly, Table 4 shows a low (good) storage modulus ratio, G′(25°C.)/G′(100° C.), for the inventive polymers of 6 or less, whereas aphysical blend (Comparative Example F*) has a storage modulus ratio of 9and a random ethylene/octene copolymer (Comparative Example G*) ofsimilar density has a storage modulus ratio an order of magnitudegreater (89). It is desirable that the storage modulus ratio of apolymer be as close to 1 as possible. Such polymers will be relativelyunaffected by temperature, and fabricated articles comprising suchpolymers can be usefully employed over a broad temperature range. Thisfeature of low storage modulus ratio and temperature independence isparticularly useful in elastomer applications such as in pressuresensitive adhesive formulations.

The data in Table 4 also demonstrate that the polymers of the inventionpossess improved pellet blocking strength. In particular, Example 5 hasa pellet blocking strength of 0 MPa, meaning it is free flowing underthe conditions tested, compared to Comparative Examples F* and G* whichshow considerable blocking. Blocking strength is important since bulkshipment of polymers having large blocking strengths can result inproduct clumping or sticking together upon storage or shipping,resulting in poor handling properties.

High temperature (70° C.) compression set for the inventive polymers isgenerally good, meaning generally less than about 80 percent, preferablyless than about 70 percent and especially less than about 60 percent. Incontrast, Comparative Examples F*, G*, H* and J* all have a 70° C.compression set of 100 percent (the maximum possible value, indicatingno recovery). Good high temperature compression set (low numericalvalues) is especially needed for applications such as gaskets, windowprofiles, o-rings, and the like. TABLE 5 Ambient Temperature MechanicalProperties Tensile 100% 300% Retractive Stress Abrasion: Notched StrainStrain Stress Com- Relaxa- Flex Tensile Tensile Elongation TensileElongation Volume Tear Recovery Recovery at 150% pression tion ModulusModulus Strength at Break¹ Strength at Break Loss Strength 21° C. 21° C.Strain Set 21° C. at 50% Ex. (MPa) (MPa) (MPa)¹ (%) (MPa) (%) (mm³) (mJ)(percent) (percent) (kPa) (Percent) Strain² D* 12 5 — — 10 1074 — — 9183 760 — — E* 895 589 — 31 1029 — — — — — — — F* 57 46 — — 12 824 93 33978 65 400 42 —  5 30 24 14 951 16 1116 48 — 87 74 790 14 33  6 33 29 — —14 938 — — — 75 861 13 —  7 44 37 15 846 14 854 39 — 82 73 810 20 —  841 35 13 785 14 810 45 461 82 74 760 22 —  9 43 38 — — 12 823 — — — — —25 — 10 23 23 — — 14 902 — — 86 75 860 12 — 11 30 26 — — 16 1090 — 97689 66 510 14 30 12 20 17 12 961 13 931 — 1247  91 75 700 17 — 13 16 14 —— 13 814 — 691 91 — — 21 — 14 212 160 — — 29 857 — — — — — — — 15 18 1412 1127  10 1573 — 2074  89 83 770 14 — 16 23 20 — — 12 968 — — 88 831040  13 — 17 20 18 — — 13 1252 — 1274  13 83 920  4 — 18 323 239 — — 30808 — — — — — — — 19 706 483 — — 36 871 — — — — — — — G* 15 15 — — 171000 — 746 86 53 110 27 50 H* 16 15 — — 15 829 — 569 87 60 380 23 — I*210 147 — — 29 697 — — — — — — — J* — — — — 32 609 — — 93 96 1900  25 —K* — — — — — — — — — — — 30 —¹Tested at 51 cm/minute²measured at 38° C. for 12 hours

Table 5 shows results for mechanical properties for the new polymers aswell as for various comparison polymers at ambient temperatures. It maybe seen that the inventive polymers have very good abrasion resistancewhen tested according to ISO 4649, generally showing a volume loss ofless than about 90 mm³, preferably less than about 80 mm³, andespecially less than about 50 mm³. In this test, higher numbers indicatehigher volume loss and consequently lower abrasion resistance.

Tear strength as measured by tensile notched tear strength of theinventive polymers is generally 1000 mJ or higher, as shown in Table 5.Tear strength for the inventive polymers can be as high as 3000 mJ, oreven as high as 5000 mJ. Comparative polymers generally have tearstrengths no higher than 750 mJ.

Table 5 also shows that the polymers of the invention have betterretractive stress at 150 percent strain (demonstrated by higherretractive stress values) than some of the comparative samples.Comparative Examples F*, G* and H* have retractive stress value at 150percent strain of 400 kPa or less, while the inventive polymers haveretractive stress values at 150 percent strain of 500 kPa (Ex. 11) to ashigh as about 1100 kPa (Ex. 17). Polymers having higher than 150 percentretractive stress values would be quite useful for elastic applications,such as elastic fibers and fabrics, especially nonwoven fabrics. Otherapplications include diaper, hygiene, and medical garment waistbandapplications, such as tabs and elastic bands.

Table 5 also shows that stress relaxation (at 50 percent strain) is alsoimproved (less) for the inventive polymers as compared to, for example,Comparative Example G*. Lower stress relaxation means that the polymerretains its force better in applications such as diapers and othergarments where retention of elastic properties over long time periods atbody temperatures is desired.

Optical Testing TABLE 6 Polymer Optical Properties Ex. Internal Haze(percent) Clarity (percent) 45° Gloss (percent) F* 84 22 49 G* 5 73 56 5 13 72 60  6 33 69 53  7 28 57 59  8 20 65 62  9 61 38 49 10 15 73 6711 13 69 67 12 8 75 72 13 7 74 69 14 59 15 62 15 11 74 66 16 39 70 65 1729 73 66 18 61 22 60 19 74 11 52 G* 5 73 56 H* 12 76 59 I* 20 75 59

The optical properties reported in Table 6 are based on compressionmolded films substantially lacking in orientation. Optical properties ofthe polymers may be varied over wide ranges, due to variation incrystallite size, resulting from variation in the quantity of chainshuttling agent employed in the polymerization.

Extractions of Multi-Block Copolymers

Extraction studies of the polymers of examples 5, 7 and ComparativeExample E* are conducted. In the experiments, the polymer sample isweighed into a glass fritted extraction thimble and fitted into aKumagawa type extractor. The extractor with sample is purged withnitrogen, and a 500 mL round bottom flask is charged with 350 mL ofdiethyl ether. The flask is then fitted to the extractor. The ether isheated while being stirred. Time is noted when the ether begins tocondense into the thimble, and the extraction is allowed to proceedunder nitrogen for 24 hours. At this time, heating is stopped and thesolution is allowed to cool. Any ether remaining in the extractor isreturned to the flask. The ether in the flask is evaporated under vacuumat ambient temperature, and the resulting solids are purged dry withnitrogen. Any residue is transferred to a weighed bottle usingsuccessive washes of hexane. The combined hexane washes are thenevaporated with another nitrogen purge, and the residue dried undervacuum overnight at 40° C. Any remaining ether in the extractor ispurged dry with nitrogen.

A second clean round bottom flask charged with 350 mL of hexane is thenconnected to the extractor. The hexane is heated to reflux with stirringand maintained at reflux for 24 hours after hexane is first noticedcondensing into the thimble. Heating is then stopped and the flask isallowed to cool. Any hexane remaining in the extractor is transferredback to the flask. The hexane is removed by evaporation under vacuum atambient temperature, and any residue remaining in the flask istransferred to a weighed bottle using successive hexane washes. Thehexane in the flask is evaporated by a nitrogen purge, and the residueis vacuum dried overnight at 40° C.

The polymer sample remaining in the thimble after the extractions istransferred from the thimble to a weighed bottle and vacuum driedovernight at 40° C. Results are contained in Table 7. TABLE 7 etherether C₈ hexane hexane C₈ residue wt. soluble soluble mole solublesoluble mole C₈ mole Sample (g) (g) (percent) percent¹ (g) (percent)percent¹ percent¹ Comp. 1.097 0.063 5.69 12.2 0.245 22.35 13.6 6.5 F*Ex. 5 1.006 0.041 4.08 — 0.040 3.98 14.2 11.6 Ex. 7 1.092 0.017 1.5913.3 0.012 1.10 11.7 9.9¹Determined by ¹³C NMRAdditional Polymer Examples 19 A-F. Continuous Solution Polymerization,Catalyst A1/B2+DEZ

Continuous solution polymerizations are carried out in a computercontrolled well-mixed reactor. Purified mixed alkanes solvent (Isopar™ Eavailable from ExxonMobil Chemical Company), ethylene, 1-octene, andhydrogen (where used) are combined and fed to a 27 gallon reactor. Thefeeds to the reactor are measured by mass-flow controllers. Thetemperature of the feed stream is controlled by use of a glycol cooledheat exchanger before entering the reactor. The catalyst componentsolutions are metered using pumps and mass flow meters. The reactor isrun liquid-full at approximately 550 psig pressure. Upon exiting thereactor, water and additive are injected in the polymer solution. Thewater hydrolyzes the catalysts, and terminates the polymerizationreactions. The post reactor solution is then heated in preparation for atwo-stage devolatization. The solvent and unreacted monomers are removedduring the devolatization process. The polymer melt is pumped to a diefor underwater pellet cutting.

Process details and results are contained in Table 8A. Selected polymerproperties are provided in Table 8B and 8C. TABLE 8A PolymerizationConditions for Polymers 19a-j Cat Cat Cat Cat A1² A1 B2³ B2 DEZ DEZ C₂H₄C₈H₁₆ Solv. H₂ T Conc. Flow Conc. Flow Conc Flow Ex. lb/hr lb/hr lb/hrsccm¹ ° C. ppm lb/hr ppm lb/hr wt % lb/hr 19a 55.29 32.03 323.03 101 120600 0.25 200 0.42 3.0 0.70 19b 53.95 28.96 325.3 577 120 600 0.25 2000.55 3.0 0.24 19c 55.53 30.97 324.37 550 120 600 0.216 200 0.609 3.00.69 19d 54.83 30.58 326.33 60 120 600 0.22 200 0.63 3.0 1.39 19e 54.9531.73 326.75 251 120 600 0.21 200 0.61 3.0 1.04 19f 50.43 34.80 330.33124 120 600 0.20 200 0.60 3.0 0.74 19g 50.25 33.08 325.61 188 120 6000.19 200 0.59 3.0 0.54 19h 50.15 34.87 318.17 58 120 600 0.21 200 0.663.0 0.70 19i 55.02 34.02 323.59 53 120 600 0.44 200 0.74 3.0 1.72 19j7.46 9.04 50.6 47 120 150 0.22 76.7 0.36 0.5 0.19 [Zn]⁴ Cocat 1 Cocat 1Cocat 2 Cocat 2 in Poly Conc. Flow Conc. Flow polymer Rate⁵ Conv⁶Polymer Ex. ppm lb/hr ppm lb/hr ppm lb/hr wt % wt % Eff.⁷ 19a 4500 0.65525 0.33 248 83.94 88.0 17.28 297 19b 4500 0.63 525 0.11 90 80.72 88.117.2 295 19c 4500 0.61 525 0.33 246 84.13 88.9 17.16 293 19d 4500 0.66525 0.66 491 82.56 88.1 17.07 280 19e 4500 0.64 525 0.49 368 84.11 88.417.43 288 19f 4500 0.52 525 0.35 257 85.31 87.5 17.09 319 19g 4500 0.51525 0.16 194 83.72 87.5 17.34 333 19h 4500 0.52 525 0.70 259 83.21 88.017.46 312 19i 4500 0.70 525 1.65 600 86.63 88.0 17.6 275 19j — — — — — —— — —¹standard cm³/min²[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl³bis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino)zirconium dimethyl⁴ppm in final product calculated by mass balance⁵polymer production rate⁶weight percent ethylene conversion in reactor⁷efficiency, kg polymer/g M where g M = g Hf + g Z

TABLE 8B Polymer Physical properties Polymer Heat of Tm- CRYSTAF Ex.Density Mw Mn Fusion Tm TCRYSTAF TCRYSTAF Peak Area No. (g/cc) I2 I10I10/I2 (g/mol) (g/mol) Mw/Mn (J/g) (° C.) Tc (° C.) (° C.) (° C.) (wt %)19g 0.8649 0.9 6.4 7.1 135000 64800 2.1 26 120 92 30 90 90 19h 0.86541.0 7.0 7.1 131600 66900 2.0 26 118 88 — — —

TABLE 8C Average Block Index For exemplary polymers¹ Example Zn/C2²Average BI Polymer F 0 0 Polymer 8 0.56 0.59 Polymer 19a 1.3 0.62Polymer 5 2.4 0.52 Polymer 19b 0.56 0.54 Polymer 19h 3.15 0.59¹Additional information regarding the measurement and calculation of theblock indices for various polymers is disclosed in U.S. patentapplication Ser. No.      (insert when known), entitled“Ethylene/α-Olefin Block Interpolymers”, filed on Mar. 15, 2006, in thename of Colin L. P. Shan, Lonnie Hazlitt, et. al. and assigned to DowGlobal Technologies Inc., the disclose of which is incorporated byreference herein in its entirety.²Zn/C2 * 1000 = (Zn feed flow * Zn concentration/1000000/Mw ofZn)/(Total Ethylene feed flow * (1 − fractional ethylene conversionrate)/Mw of Ethylene) * 1000. Please note that “Zn” in “Zn/C2 * 1000”refers to the amount of zinc in diethyl zinc (“DEZ”) used in thepolymerization process, and “C2” refers to the amount of ethylene usedin the polymerization process.Procedure for Making Polymer Example 20

The procedure for making Polymer Example 20 used in the followingexamples is as follows: A single one gallon autoclave continuouslystirred tank reactor (CSTR) was employed for the experiments. Thereactor runs liquid full at ca. 540 psig with process flow in the bottomand out the top. The reactor is oil jacketed to help remove some of theheat of reaction. Primary temperature control is achieved by two heatexchangers on the solvent/ethylene addition line. ISOPAR® E, hydrogen,ethylene, and 1-octene were supplied to the reactor at controlled feedrates.

Catalyst components were diluted in an air-free glove box. The twocatalysts were fed individually at the desired ratio from differentholding tanks. To avoid catalyst feed line plugging, the catalyst andcocatalyst lines were split and fed separately into the reactor. Thecocatalyst was mixed with the diethylzinc chain shuttling agent beforeentry into the reactor.

The prime product was collected under stable reactor conditions. Afterseveral hour, the product samples showed no substantial change in meltindex or density. The products were stabilized with a mixture ofIRGANOX® 1010, IRGANOX® 1076 and IRGAFOS® 176. Temperature C₂ flow C₈flow H₂ flow Density I₂ I₁₀/I₂ (° C.) (kg/hr) (kg/hr) (sccm) 0.8540 1.0537.90 120.0 0.600 5.374 0.9 Catalyst Efficiency A1 C₂ Polymer (kgCatalyst A1 Catalyst conversion C₈ conversion % production polymer/gFlow Concentration (%) (%) solids rate (kg/hr) total metal) (kg/hr)(ppm) 89.9 20.263 10.0 1.63 287 0.043 88.099 A2 Catalyst A2 CatalystRIBS-2 DEZ DEZ Flow Concentration Mole % RIBS-2 Flow Concentration flowconcentration (kg/hr) (ppm) A2 (kg/hr) (ppm) (kg/hr) (ppm Zn) 0.1969.819 50.039 0.063 1417 0.159 348

The structures for the two catalysts used in the above procedures (i.e.,Catalysts A1 and A2) are shown below:

Blend Examples

Blend compositions comprising Polymer Example 20, a randomethylene/1-octene copolymer and polypropylene (PP1) were prepared,evaluated and tested for properties. The following polymers werecompared in blend compositions.

Polymer Example 20 is an ethylene/1-octene block copolymer having acomposite 1-octene content of 77 wt. %, a composite density of 0.854g/cc, a DSC peak melting point of 105° C., a hard segment level basedupon DSC measurement of 6.8 wt. %, an ATREF crystallization temperatureof 73° C., a number average molecular weight of 188,254 daltons, aweight average molecular weight of 329,600 daltons, a melt index at 190°C., 2.16 Kg of 1.0 dg/min and a melt index at 190° C., 10 Kg of 37.0dg/min. The polymer of Example 20 is prepared as described above.

Comparative Example A¹ is a random ethylene/1-octene copolymer having adensity of 0.87 g/cc, a 1-octene content of 38 wt. %, a peak meltingpoint of 59.7° C., a number average molecular weight of 59,000 daltons,a weight average molecular weight of 121,300 daltons, a melt index of1.0 dg/min at 190° C., 2.16 Kg and a melt index at 190° C., 10 Kg of 7.5dg/min. The product is commercially available under the tradenameEngage® 8100 from The Dow Chemical Company.

The above polymers were melt mixed with PP1, a polypropylene homopolymerhaving a melt flow index at 230° C., 2.16 Kg of 2.0 dg/min, a DSCmelting point of 161° C., and a density of 0.9 g/cc. The product iscommercially available The Dow Chemical Company under the commercialname of Dow Polypropylene H110-02N. For all blends, 0.2 parts per 100total polymer of a 1:1 blend of phenolic/phosphite antioxidant,available under the tradename Irganox® B2 15, was added for heatstability. This additive is designated as AO in Table 9.

The following mixing procedure was used. A 69 cc capacity Haake batchmixing bowl fitted with roller blades was heated to 200° C. for allzones. The mixing bowl rotor speed was set at 30 rpm and was chargedwith PP1, allowed to flux for one minute, then charged with AO andfluxed for an additional two minutes. The mixing bowl was then chargedwith either polymer Example 20, Comparative Example A¹, or a 1:1 blendof polymer Example 20 and Comparative Example A¹. After adding theelastomer, the mixing bowl rotor speed was increased to 60 rpm andallowed to mix for an additional 3 minutes. The mixture was then removedfrom the mixing bowl and pressed between Mylar sheets sandwiched betweenmetal platens and compressed in a Carver compression molding machine setto cool at 15° C. with a pressure of 20 kpsi. The cooled mixture wasthen compression molded into 2 inch×2 inch×0.06 inch plaques viacompression molding for 3 minutes at 190° C., 2 kpsi pressure for 3minutes, 190° C., 20 kpsi pressure for 3 minutes, then cooling at 15°C., 20 kpsi for 3 minutes. The mixtures prepared under the proceduredescribed above are listed in Table 9. TABLE 9 Comparative Blends withPP Mixture 1 Mixture 2 Mixture 3 Ingredient Parts parts parts PP1 70 7070 Polymer Example 20 30 0 15 Comparative Example A¹ 0 30 15 AO 0.2 0.20.2

Compression molded plaques were trimmed so that sections could becollected at the core. The trimmed plaques were cryopolished prior tostaining by removing sections from the blocks at −60° C. to preventsmearing of the elastomer phases. The cryo-polished blocks were stainedwith the vapor phase of a 2% aqueous ruthenium tetraoxide solution for 3hours at ambient temperature. The staining solution was prepared byweighing 0.2 gm of ruthenium (III) chloride hydrate (RuCl₃×H₂O) into aglass bottle with a screw lid and adding 10 ml of 5.25% aqueous sodiumhypochlorite to the jar. The samples were placed in the glass jar usinga glass slide having double sided tape. The slide was placed in thebottle in order to suspend the blocks about 1 inch above the stainingsolution. Sections of approximately 100 nanometers in thickness werecollected at ambient temperature using a diamond knife on a Leica EM UC6microtome and placed on 400 mesh virgin TEM grids for observation.

Bright-field images were collected on a JEOL JEM 1230 TransmissionElectron Microscope operated at 100 kV accelerating voltage andcollected using Gatan 791 and Gatan 794 digital cameras. The images werepost processed using Adobe Photoshop 7.0.

FIGS. 8 and 9 are transmission electron micrographs of Mixture 1 andMixture 2, respectively. The dark domains are the RuCl₃ XH₂O stainedethylene/1-octene polymers. As can be seen, the domains containingPolymer example 20 are much smaller than Comparative Example A¹. Thedomain sizes for Polymer example 20 range from about 0.1 to about 2 μm,whereas the domain sizes for Comparative Example A¹ from about 0.2 toover 5 μm. Mixture 3 contains a 1:1 blend of Polymer example 20 andComparative Example A¹. It is noted that by visual inspection the domainsizes for Mixture 3 are well below those for Mixture 2, indicating thatPolymer example 20 is improving the compatibility of Comparative ExampleA¹ with PP 1.

Image analysis of Mixtures 1, 2, and 3 was performed using Leica QwinPro V2.4 software on 5 k× TEM images. The magnification selected forimage analysis depended on the number and size of particles to beanalyzed. In order to allow for binary image generation, manual tracingof the elastomer particles from the TEM prints was carried out using ablack Sharpie marker. The traced TEM images were scanned using a HewlettPackard Scan Jet 4c to generate digital images. The digital images wereimported into the Leica Qwin Pro V2.4 program and converted to binaryimages by setting a gray-level threshold to include the features ofinterest. Once the binary images were generated, other processing toolswere used to edit images prior to image analysis. Some of these featuresincluded removing edge features, accepting or excluding features, andmanually cutting features that required separation. Once the particlesin the images were measured, the sizing data was exported into an Excelspreadsheet that was used to create bin ranges for the rubber particles.The sizing data was placed into appropriate bin ranges and a histogramof particle lengths (maximum particle length) versus percent frequencywas generated. Parameters reported were minimum, maximum, averageparticle size and standard deviation. Table 10 shows the results of theimage analysis TABLE 10 Image Analysis of Mixture Domains Sizes MixtureNumber 1 2 3 Number of Count 718 254 576 Maximum Domain Size, mm 5.115.3 2.9 Minimum Domain Size, mm 0.3 0.3 0.3 Mean Domain Size, mm 0.81.9 0.8 Standard Deviation, mm 0.5 2.2 0.4

The results show that that both Mixtures 1 and 2 exhibited lower meanelastomer domain size and narrower domain size distribution. Thebeneficial interfacial effect from Polymer example 20 can be seen as a1:1 blend with Comparative Example A¹ in Mixture 3. The resultant domainmean particle size and range are nearly identical to Mixture 1, whichcontains only Polymer example 20 as the elastomer.

As demonstrated above, embodiments of the invention provides variouspolymer blends with improved compatibility. The improved compatibilityis obtained by adding the inventive block interpolymer to a mixture oftwo or more polyolefins which are otherwise relatively immiscible. Theimproved compatibility is evidenced by a reduction of the average domainsize and more uniform mixing. Such blends should exhibit synergisticeffects in the blend's physical properties.

While the invention has been described with respect to a limited numberof embodiments, the specific features of one embodiment should not beattributed to other embodiments of the invention. No single embodimentis representative of all aspects of the invention. In some embodiments,the compositions or methods may include numerous compounds or steps notmentioned herein. In other embodiments, the compositions or methods donot include, or are substantially free of, any compounds or steps notenumerated herein. Variations and modifications from the describedembodiments exist. Finally, any number disclosed herein should beconstrued to mean approximate, regardless of whether the word “about” or“approximately” is used in describing the number. The appended claimsintend to cover all those modifications and variations as falling withinthe scope of the invention.

1. A polymer blend comprising: (i) a first polyolefin; (ii) a secondpolyolefin; and (iii) an ethylene/α-olefin interpolymer, wherein thefirst polyolefin, the second polyolefin and the ethylene/α-olefininterpolymer are different and wherein the ethylene/α-olefininterpolymer: (a) has a M_(w)/M_(n) from about 1.7 to about 3.5, atleast one melting point, Tm, in degrees Celsius, and a density, d, ingrams/cubic centimeter, wherein the numerical values of Tm and dcorrespond to the relationship:T _(m)>−2002.9+4538.5(d)−2422.2(d)², or (b) has a M_(w)/M_(n) from about1.7 to about 3.5, and is characterized by a heat of fusion, ΔH in J/g,and a delta quantity, ΔT, in degrees Celsius defined as the temperaturedifference between the tallest DSC peak and the tallest CRYSTAF peak,wherein the numerical values of ΔT and ΔH have the followingrelationships:ΔT>−0.1299(ΔH)+62.81 for ΔH greater than zero and up to 130 J/g,ΔT≧48° C. for ΔH greater than 130 J/g, wherein the CRYSTAF peak isdetermined using at least 5 percent of the cumulative polymer, and ifless than 5 percent of the polymer has an identifiable CRYSTAF peak,then the CRYSTAF temperature is 30° C.; or (c) is characterized by anelastic recovery, Re, in percent at 300 percent strain and I cyclemeasured with a compression-molded film of the ethylene/α-olefininterpolymer, and has a density, d, in grams/cubic centimeter, whereinthe numerical values of Re and d satisfy the following relationship whenthe ethylene/α-olefin interpolymer is substantially free of across-linked phase:Re>1481-1629(d); or (d) has a molecular fraction which elutes between40° C. and 130° C. when fractionated using TREF, characterized in thatthe fraction has a molar comonomer content of at least 5 percent higherthan that of a comparable random ethylene interpolymer fraction elutingbetween the same temperatures, wherein said comparable random ethyleneinterpolymer has the same comonomer(s) and has a melt index, density,and molar comonomer content (based on the whole polymer) within 10percent of that of the ethylene/α-olefin interpolymer; or (e) has astorage modulus at 25° C., G′(25° C.), and a storage modulus at 100° C.,G′(100° C.), wherein the ratio of G′(25° C.) to G′(100° C.) is in therange of about 1:1 to about 9:1.
 2. The polymer blend of claim 1,wherein the ethylene/α-olefin interpolymer has a M_(w)/M_(n) from about1.7 to about 3.5, at least one melting point, Tm, in degrees Celsius,and a density, d, in grams/cubic centimeter, wherein the numericalvalues of Tm and d correspond to the relationship:Tm≧858.91-1825.3(d)+1112.8(d)².
 3. The polymer blend of claim 1, whereinthe ethylene/α-olefin interpolymer has a M_(w)/M_(n) from about 1.7 toabout 3.5 and is characterized by a heat of fusion, ΔH in J/g, and adelta quantity, ΔT, in degrees Celsius defined as the temperaturedifference between the tallest DSC peak and the tallest CRYSTAF peak,wherein the numerical values of ΔT and ΔH have the followingrelationships:ΔT>−0.1299(ΔH)+62.81 for ΔH greater than zero and up to 130 J/g,ΔT≧48° C. for ΔH greater than 130 J/g, wherein the CRYSTAF peak isdetermined using at least 5 percent of the cumulative polymer, and ifless than 5 percent of the polymer has an identifiable CRYSTAF peak,then the CRYSTAF temperature is 30° C.
 4. The polymer blend of claim 1,wherein the ethylene/α-olefin interpolymer is characterized by anelastic recovery, Re, in percent at 300 percent strain and 1 cyclemeasured with a compression-molded film of the ethylene/α-olefininterpolymer, and has a density, d, in grams/cubic centimeter, whereinthe numerical values of Re and d satisfy the following relationship whenthe ethylene/α-olefin interpolymer is substantially free of across-linked phase:Re>1481-1629(d).
 5. The polymer blend of claim 4, wherein the numericalvalues of Re and d satisfy the following relationship:Re>1491-1629(d).
 6. The polymer blend of claim 4, wherein the numericalvalues of Re and d satisfy the following relationship:Re>1501-1629(d).
 7. The polymer blend of claim 4, wherein the numericalvalues of Re and d satisfy the following relationship:Re>1511-1629(d).
 8. The polymer blend of claim 1, wherein theethylene/α-olefin interpolymer has a molecular fraction which elutesbetween 40° C. and 130° C. when fractionated using TREF, characterizedin that the fraction has a molar comonomer content of at least 5 percenthigher than that of a comparable random ethylene interpolymer fractioneluting between the same temperatures, wherein said comparable randomethylene interpolymer has the same comonomer(s) and has a melt index,density, and molar comonomer content (based on the whole polymer) within10 percent of that of the ethylene/α-olefin interpolymer.
 9. The polymerblend of claim 1, wherein the ethylene/α-olefin interpolymer has astorage modulus at 25° C., G′(25° C.), and a storage modulus at 100° C.,G′(100° C.), wherein the ratio of G′(25° C.) to G′(100° C.) is in therange of about 1:1 to about 9:1.
 10. The polymer blend of claim 1,wherein the ethylene/α-olefin interpolymer is an elastomeric polymerhaving an ethylene content of from 5 to 95 mole percent, a diene contentof from 5 to 95 mole percent, and an α-olefin content of from 5 to 95mole percent.
 11. The polymer blend of claim 1, wherein the firstpolyolefin is an olefin homopolymer.
 12. The polymer blend of claim 11,wherein the olefin homopolymer is a polypropylene.
 13. The polymer blendof claim 12, wherein the polypropylene is low density polypropylene(LDPP), high density polypropylene (HDPP), high melt strengthpolypropylene (HMS-PP), high impact polypropylene (HIPP), isotacticpolypropylene (iPP), syndiotactic polypropylene (sPP) or a combinationthereof.
 14. The polymer blend of claim 13, wherein the polypropylene isisotactic polypropylene.
 15. The polymer blend of claim 1, wherein thesecond polyolefin is an olefin copolymer, an olefin terpolymer or acombination thereof.
 16. The polymer blend of claim 15, wherein theolefin copolymer is an ethylene/propylene copolymer (EPM).
 17. Thepolymer blend of claim 15, wherein the olefin terpolymer is derived fromethylene, a monoene having 3 or more carbon atoms or a diene.
 18. Thepolymer blend of claim 1, wherein the second polyolefin is avulcanizable rubber.
 19. A molded article comprising the polymer blendof claim
 1. 20. The molded article of claim 19, wherein the moldedarticle is a tire, a hose, a belt, a gasket, a shoe sole, a molding or amolded part.
 21. A sheet article comprising at least one layercomprising the polymer blend of claim
 1. 22. A thermoformed articlecomprising the sheet of claim
 21. 23. A profile article comprising atleast one layer comprising the polymer blend of claim
 1. 24. A polymerblend comprising: (i) a first polyolefin; (ii) a second polyolefin; and(iii) an ethylene/α-olefin interpolymer, wherein the first polyolefin,the second polyolefin and the ethylene/α-olefin interpolymer aredifferent and wherein the ethylene/α-olefin interpolymer: (a) has atleast one molecular fraction which elutes between 40° C. and 130° C.when fractionated using TREF, characterized in that the fraction has ablock index of at least 0.5 and up to about 1 and a molecular weightdistribution, Mw/Mn, greater than about 1.3 or (b) has an average blockindex greater than zero and up to about 1.0 and a molecular weightdistribution, Mw/Mn, greater than about 1.3.
 25. The polymer blend ofclaim 24, wherein the ethylene/α-olefin interpolymer has at least onemolecular fraction which elutes between 40° C. and 130° C. whenfractionated using TREF, characterized in that the fraction has a blockindex of at least 0.5 and up to about 1 and a molecular weightdistribution, Mw/Mn, greater than about 1.3.
 26. The polymer blend ofclaim 24, wherein the ethylene/α-olefin interpolymer an average blockindex greater than zero and up to about 1.0 and a molecular weightdistribution, Mw/Mn, greater than about 1.3.
 27. The polymer blend ofclaim 24, wherein the ethylene/α-olefin interpolymer is an elastomericpolymer having an ethylene content of from 5 to 95 mole percent, a dienecontent of from 5 to 95 mole percent, and an α-olefin content of from 5to 95 mole percent.
 28. The polymer blend of claim 24, wherein the firstpolyolefin is an olefin homopolymer.
 29. The polymer blend of claim 28,wherein the olefin homopolymer is a polypropylene.
 30. The polymer blendof claim 29, wherein the polypropylene is low density polypropylene(LDPP), high density polypropylene (HDPP), high melt strengthpolypropylene (HMS-PP), high impact polypropylene (HIPP), isotacticpolypropylene (iPP), syndiotactic polypropylene (sPP) or a combinationthereof.
 31. The polymer blend of claim 29, wherein the polypropylene isisotactic polypropylene.
 32. The polymer blend of claim 24, wherein thesecond polyolefin is an olefin copolymer, an olefin terpolymer or acombination thereof.
 33. The polymer blend of claim 32, wherein theolefin copolymer is an ethylene/propylene copolymer (EPM).
 34. Thepolymer blend of claim 32, wherein the olefin terpolymer is derived fromethylene, a monoene having 3 or more carbon atoms or a diene.
 35. Thepolymer blend of claim 24, wherein the second polyolefin is avulcanizable rubber.
 36. A molded article comprising the polymer blendof claim
 24. 37. The molded article of claim 36, wherein the moldedarticle is a tire, a hose, a belt, a gasket, a shoe sole, a molding or amolded part.
 38. A sheet article comprising at least one layercomprising the polymer blend of claim
 24. 39. A thermoformed articlecomprising the sheet of claim
 38. 40. A profile article comprising atleast one layer comprising the polymer blend of claim 24.